Impact resistance polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiers

ABSTRACT

Polymer blends that exhibit good impact resistance comprise a crystalline polypropylene matrix and a partly crystalline copolymer impact modifier with a molecular weight lower than that of the matrix polymer. The matrix polymer can comprise any crystalline propylene homo- or copolymer. The impact modifying copolymers are characterized as comprising at least about 60 weight percent (wt %) of units derived from propylene and, in certain embodiments, as having at least one, preferably two or more, of the following properties: (i)  13 C NMR peaks corresponding to a regio-error at about 14.6 and about 15.7 ppm, the peaks of about equal intensity, (ii) a B-value greater than about 1.4 when the comonomer content of the copolymer is at least about 3 wt %, (iii) a skewness index, S ix , greater than about −1.20, (iv) a DSC curve with a T me  that remains essentially the same and a T max  that decreases as the amount of comonomer in the copolymer is increased, and (v) an X-ray diffraction pattern that reports more gamma-form crystals than a comparable copolymer prepared with a Ziegler-Natta (Z-N) catalyst.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.10/884,420, filed Jul. 2, 2004, and now U.S. Pat. No. 7,109,269 which isa division of U.S. patent application Ser. No. 10/289,122, filed Nov. 5,2002, and now U.S. Pat. No. 6,943,215 which also claims the benefitunder 35 USC §119(e) of U.S. Provisional Application Nos. 60/338,881 and60/378,203 filed Nov. 6, 2001 and May 5, 2002.

FIELD OF THE INVENTION

This invention relates to polymer blends. In one aspect, the inventionrelates to polymer blends comprising a polypropylene matrix and animpact modifier while in another aspect, the invention relates topolymer blends in which the matrix comprises an isotactic homopolymer ofpropylene and the impact modifier comprises an isotactic copolymer ofpropylene, ethylene and/or one or more unsaturated comonomers. In yetanother aspect, the invention relates to processes for preparing andusing the polypropylene impact copolymers, and articles made from thecopolymers.

BACKGROUND OF THE INVENTION

Crystalline polypropylene, typically a homopolymer, is used extensivelyin various moldings because it exhibits desirable mechanical (e.g.,rigidity) and chemical resistance properties. For applications thatrequire impact resistance (e.g., automobile parts, appliance facia,packaging, etc.), a rubber, e.g., copolymer of propylene and ethyleneand/or one or more α-olefins, is used, or a blend of crystallinepolypropylene with one or more rubbers that exhibit good impactresistance, e.g., propylene/ethylene (P/E) copolymer, orethylene-propylene (EP) and/or ethylene-propylene-diene (EPDM) rubber.Crystalline polypropylene has an isotactic structure, and it is readilyproduced using a Ziegler-Natta (Z-N) or a metallocene catalyst, or aconstrained geometry catalyst (CGC). For purposes of this disclosure,P/E copolymers comprise 50 weight percent or more propylene while EPcopolymers comprise 51 weight percent or more ethylene. As here used,“comprise . . . propylene”, “comprise . . . ethylene” and similar termsmean that the polymer comprises units derived from propylene, ethyleneor the like as opposed to the compounds themselves.

Polypropylene impact compositions typically comprise (i) one or orematrix polymers, e.g., a crystalline polypropylene homo- or copolymer,and (ii) one or more impact modifiers, typically a rubber. The matrixprovides the stiffness and optical properties, and the impact modifierprovides the toughness. The addition of an impact modifier generallycauses a reduction in stiffness and optics of the total blend comparedto the stiffness and optics of the matrix by itself. This reduction inoptics can be minimized by carefully designing the solubility of theimpact modifier with regard to the matrix.

The solubility of a propylene-ethylene impact modifier in the matrix isdetermined by composition and molecular weight. To achieve sufficienttoughness, a minimal level of ethylene is required in thepropylene-ethylene impact modifier, which then leaves the molecularweight as the parameter to influence solubility. Decreasing molecularweight of the impact modifier increases the solubility of the impactmodifier in the matrix. However, impact modifiers with low molecularweight may migrate to the surface of fabricated parts and show bloomingwhich can reduce the optic performance significantly.

The addition of the impact modifier can be in-situ (e.g., reactors inseries) or off-line via compounding (e.g., physically blending thematrix and impact modifying resins). Impact modifiers can be moreaccurately designed via single site catalysis (e.g., by a metallocene)than via Ziegler-Natta catalysis. Additionally, impact modifiersprepared via single site catalysis have a narrow molecular weightdistribution (MWD), and thus have less low molecular weight extractablesthan impact modifiers prepared via Ziegler-Natta catalysis.

SUMMARY OF THE INVENTION

According to this invention, polymer blends that exhibit good impactresistance comprise a (i) crystalline polypropylene matrix, and (ii)partially crystalline copolymer impact modifier that has a molecularweight lower than that of the matix polymer. The matrix polymer cancomprise any crystalline propylene homo- or copolymer. The impactmodifier is a polymer, typically a copolymer or terpolymer, of propyleneand ethylene and/or one or more unsaturated comonomers, e.g., C₄₋₂₀α-olefins, C₄₋₂₀ dienes, styrenic compounds, etc. Impact modifiers ofpropylene and ethylene and/or one or more unsaturated comonomers aretypically prepared using a (i) metallocene catalyst, or (iii)nonmetallocene, metal-centered, heteroaryl ligand catalyst. Impactmodifiers of propylene and ethylene and/or one or more unsaturatedcomonomers prepared using a nonmetallocene, metal-centered, heteroarylligand catalyst are designated in this disclosure as P/E* copolymers.

Typically, the crystalline polypropylene matrix comprises at least about50 percent by weight of the polymer blend. If clarity and/or stiffnessare the important properties of the blend, then the crystallinepolypropylene comprises at least about 60, preferably at least about 70and more preferably at least about 80, weight percent of the blend basedupon the total weight of the blend.

In a first embodiment, the impact modifying polymers have at least oneof a (i) percent crystallinity (defined as 100×the heat of fusion asdetermined by DSC divided by 165 J/g) typically of about 55 to greaterthan (>) 0, preferably of about 50 to >0, more preferably of about 45to >0, and even more preferably of about 40 to >0, (ii) melt flow rate(MFR) typically of about 0.01 to about 1000, preferably of about 0.02 toabout 100, more preferably of about 0.02 to about 80, and even morepreferably of about 0.02 to 50, and (iii) an MWD narrower than acomparable polymer prepared with a Ziegler-Natta (Z-N) catalyst. “Acomparable polymer” has the same meaning as it does for the X-rayproperty defined below. Typically, the percent crystallinity of theimpact modifying polymers is at least about 0.1, preferably at leastabout 1 and more preferably at least about 3.

In a second embodiment, the impact modifier is a copolymer or terpolymerof propylene, ethylene and, optionally, one or more unsaturatedcomonomers, e.g., C₄₋₂₀ α-olefins, C₄₋₂₀ dienes, vinyl aromaticcompounds (e.g., styrene), etc. These polymers are characterized ascomprising at least about 60 weight percent (wt %) of units derived frompropylene, about 0.1-35 wt % of units derived from ethylene, and 0 toabout 35 wt % of units derived from one or more unsaturated comonomers,with the proviso that the combined weight percent of units derived fromethylene and the unsaturated comonomer does not exceed about 40. Thesepolymers are also characterized as having at least one of the followingproperties: (i) ¹³C NMR peaks corresponding to a regio-error at about14.6 and about 15.7 ppm, the peaks of about equal intensity, (ii) aB-value greater than about 1.4 when the comonomer content, i.e., theunits derived from ethylene and/or the unsaturated comonomer(s), of thepolymer is at least about 3 wt %, (iii) a skewness index, S_(ix),greater than about −1.20, (iv) a DSC curve with a T_(me) that remainsessentially the same and a T_(max) that decreases as the amount ofcomonomer, i.e., the units derived from ethylene and/or the unsaturatedcomonomer(s), in the polymer is increased, and (v) an X-ray diffractionpattern that reports more gamma-form crystals than a comparable polymerprepared with a Ziegler-Natta (Z-N) catalyst. Typically the polymers ofthis embodiment are characterized by at least two of these properties.Certain of the polymers of this embodiment are characterized by at leastthree of these properties, while other polymers of this embodiment arecharacterized by at least four or even all five of these properties.

With respect to the X-ray property of subparagraph (v) above, “acomparable polymer” is one having the same monomer composition within 10wt %, and the same Mw within 10 wt %. For example, if apropylene/ethylene/1-hexene terpolymer is 9 wt % ethylene and 1 wt %1-hexene and has a Mw of 250,000, then a comparable polymer would havefrom 8.1-9.9 wt % ethylene, 0.9-1.1 wt % 1-hexene, and a Mw between225,000 and 275,000, prepared with a Ziegler-Natta catalyst.

In a third embodiment, the impact modifier is a polymer, typically acopolymer or terpolymer, of propylene and one or more unsaturatedcomonomers. These polymers are characterized in having at least about 60wt % of the units derived from propylene, and between about 0.1 and 40wt % the units derived from the unsaturated comonomer. These polymersare also characterized as having at least one of the followingproperties: (i) ¹³C NMR peaks corresponding to a regio-error at about14.6 and about 15.7 ppm, the peaks of about equal intensity, (ii) aB-value greater than about 1.4 when the comonomer content, i.e., theunits derived from the unsaturated comonomer(s), of the polymer is atleast about 3 wt %, (iii) a skewness index, S_(ix), greater than about−1.20, (iv) a DSC curve with a T_(me) that remains essentially the sameand a T_(max) that decreases as the amount of comonomer, i.e., the unitsderived from the unsaturated comonomer(s), in the polymer is increased,and (v) an X-ray diffraction pattern that reports more gamma-formcrystals than a comparable polymer prepared with a Ziegler-Natta (Z-N)catalyst. Typically the polymers of this embodiment are characterized byat least two of these properties. Certain of the polymers of thisembodiment are characterized by at least three of these properties,while other copolymers of this embodiment are characterized by at leastfour or even all five of these properties.

In a fourth embodiment, the invention is a blend in which the matrixpolypropylene is characterized as having a ¹³C NMR peaks correspondingto a regio-error at about 14.6 and about 15.7 ppm, the peaks of aboutequal intensity and, optionally, substantially isotactic propylenesequences, i.e., the sequences have an isotactic triad (mm) measured by¹³C NMR of greater than about 0.85. These propylene homopolymerstypically have at least 50 percent more of this regio-error than acomparable polypropylene homopolymer prepared with a Ziegler-Nattacatalyst. A “comparable” polypropylene as here used means an isotacticpropylene homopolymer having the same weight average molecular weight,i.e., within plus or minus 10 wt %. In this disclosure, occasionallythese propylene homopolymers are referred to as “P* homopolymers” or asimilar term. The impact modifier of this embodiment is at least onepolymer of the propylene/ethylene and propylene/unsaturated comomonerpolymers described in the second and third embodiments of this invention(occasionally referred to in this disclosure, individually andcollectively, as a “P/E* copolymer” or a similar term). The blend is, ofcourse, a heterophasic mix in which the polypropylene matrix polymer isthe continuous phase and the impact modifying polymer is thediscontinuous or dispersed phase. P/E* copolymers are a unique subset ofP/E copolymers.

In a fifth embodiment, one or both blend components is itself a blend ofone or more polymers. The polypropylene matrix polymer can be a blend oftwo or more polypropylenes (either or both of which are homo- orcopolymers), and either or both of which can exhibit ¹³C NMR peakscorresponding to a regio-error at about 14.6 and about 15.7 ppm, thepeaks of about equal intensity and, optionally, substantially isotacticpropylene sequences. The relative amounts of each can vary widely.Alternatively, the polypropylene matrix polymer can be a blend of two ormore crystalline polypropylenes in combination with one or more othercrystalline polymers, e.g., high density polyethylene (HDPE). In thisembodiment, the other crystalline polymer is sufficiently compatiblewith the crystalline polypropylene such that the blend of these matrixpolymers form a substantially homogeneous continuous phase when incombination with the impact modifying copolymer. Typically, thecrystalline polypropylene comprises at least about 50 percent by weightof the matrix polymer blend.

Similarly, the impact modifying copolymer can be a blend of two or moreP/E* copolymers, or one or more P/E* copolymers in combination with oneor more other polymers, e.g., an EP or EPDM rubber. The relative amountsof each component of the these blends can also vary widely, althoughpreferably the one or more P/E* polymer comprises at least about 50percent by weight of the impact modifying polymer blend. Unlike thecrystalline matrix polymers, the one or more other impact modifyingpolymer need not be compatible with the one or more P/E* polymers suchthat they form a substantially homogeneous blend. Since the impactmodifying polymers form the dispersed phase within the polypropylenematrix, each impact modifying polymer component can be dispersedseparately from one another and/or as a blend of two or more of eachother.

In certain embodiments of the invention, blends comprising a crystallinepolypropylene matrix and a P/E* impact modifier do not show blooming. Incontrast, blends comprising a crystalline polypropylene matrix and anamorphous propylene/ethylene (P/E) impact modifier (containing the samelevel of ethylene and having the same low molecular weight) do showblooming.

Polypropylene-P/E* polymer blends exhibit much better optics thanpolypropylene impact polymer blends containing other P/E impactmodifiers, such as those prepared via single site catalysis, e.g., witha metallocene, in which the impact modifiers contain the same amount ofethylene. Moreover, certain impact modifying terpolymers exhibit lowerhaze values than their comparable copolymer counterparts when blendedwith a crystalline polypropylene in similar amounts and under similarconditions. Additionally, polypropylene-P/E* impact polymer blendsexhibit better stiffness than polypropylene/impact polymer blendscontaining P/E impact modifiers (in which both impact modifiers containthe same amount of ethylene).

In a sixth embodiment, the invention is the use of thepolypropylene/impact polymer blends of this invention to make variousfabricated articles, particularly molded articles.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the unusual comonomer distribution of apropylene/ethylene (P/E*) copolymer made with a metal-centered,heteroaryl ligand catalyst.

FIGS. 2A and 2B show a comparison of the DSC heating traces of thepropylene/ethylene (P/E) copolymer of Comparative Example 1 and the P/E*copolymer of Example 2, respectively.

FIG. 3 shows a comparison of the Tg data of a P/E* copolymer and aconventional Ziegler-Natta (Z-N) catalyzed P/E copolymer at equivalentcrystallinity.

FIG. 4 shows a comparison of the Tg data of a P/E* copolymer and aconventional constrained geometry catalyst (CGC) P/E copolymer at thesame ethylene content.

FIG. 5 shows a comparison of a TREF curve for a conventionalmetallocene-catalyzed P/E copolymer and a P/E* copolymer.

FIG. 6 shows the ¹³C NMR spectrum of the P* homopolymer product ofExample 7, prepared using Catalyst G. This spectrum shows the highdegree of isotacticity of the product.

FIG. 7 shows the ¹³C NMR spectrum of the P* homopolymer product ofExample 8 prepared using Catalyst H. This spectrum is shown at anexpanded Y-axis scale relative to FIG. 6 in order to more clearly showthe regio-error peaks.

FIG. 8 shows the ¹³C NMR Spectrum of the P/E* copolymer product ofExample 2 prepared using Catalyst G.

FIG. 9 shows the ¹³C NMR Spectrum of the P/E copolymer product ofComparative Example 1 prepared using metallocene Catalyst Edemonstrating the absence of regio-error peaks in the region around 15ppm.

FIGS. 10A-J show the chemical structures of various catalysts.

FIGS. 11A-B show the DSC heating and cooling traces of the P*homopolymer of Example 8, prepared using Catalyst H.

FIG. 12 shows a comparison of the skewness index for the P/E* copolymerand several P/E copolymers.

FIG. 13 compares the melting endotherms of Samples 8 and 22a of Example11.

FIG. 14 demonstrates the shift in peak melting temperature towards lowertemperature for samples of the copolymers of Example 11.

FIG. 15 is a plot of the temperature at which approximately 1 percentcrystallinity remains in DSC samples of Example 11.

FIG. 16 shows the variance relative to the first moment of the meltingendotherm as a function of the heat of melting of various samples ofExample 11.

FIG. 17 shows the maximum heat flow normalized by the heat of melting asa function of the heat of melting for various samples of Example 11.

FIG. 18 illustrates that the rate at which the last portion ofcrystallinity disappears in the P/E* polymers is significantly lowerthan for metallocene polymers.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Crystalline Polypropylene Matrix

The polypropylene used as the matrix polymer in the practice of thisinvention can be any suitable crystalline propylene homopolymer orcopolymer. If a copolymer, typically it contains less than 20, morepreferably less than 10 and even more preferably less than about 5, molepercent comonomer, e.g., an α-olefin having up to about 20, preferablyup to about 12 and more preferably up to about 8, carbon atoms.Typically the α-olefin is ethylene. If the polypropylene is a copolymer,then it can be random, block or graft. If the matrix is a blend ofpropylene polymers, the amount of each component of the blend can varywidely ranging from 100 weight percent homopolymer, to a blend of ahomopolymer with one or more crystalline propylene copolymers, to 100weight percent propylene copolymer. While the matrix may comprise P*homopolymer, preferably the matrix comprises a majority, more preferablya substantial majority, of a highly crystalline polypropylene preparedby Ziegler-Natta or metallocene catalysis.

Impact Modifying Polymer

One species of impact modifying polymers of this invention are propylenepolymers that comprise propylene, ethylene and, optionally, one or moreunsaturated comonomers. This species includes both P/E and P/E*polymers. Typically, these polymers comprise units derived frompropylene in an amount of at least about 60, preferably at least about80 and more preferably at least about 85, wt % of the polymer. Thetypical amount of ethylene in these polymers is at least about 0.1,preferably at least about 1 and more preferably at least about 5 wt %,and the maximum amount of units derived from ethylene present in thesepolymers is typically not in excess of about 35, preferably not inexcess of about 30 and more preferably not in excess of about 20, wt %of the polymer. The amount of units derived from the unsaturatedcomonomer(s), if present, is typically at least about 0.01, preferablyat least about 1 and more preferably at least about 5, wt %, and thetypical maximum amount of units derived from the unsaturatedcomonomer(s) typically does not exceed about 35, preferably it does notexceed about 30 and more preferably it does not exceed about 20, wt % ofthe polymer. The combined total of units derived from ethylene and anyunsaturated comonomer typically does not exceed about 40, preferably itdoes not exceed about 30 and more preferably it does not exceed about20, wt % of the polymer.

Another species of impact modifying polymers of this invention comprisepropylene and one or more unsaturated comonomers (other than ethylene).This species also includes both P/E and P/E* polymers. These polymersalso typically comprise units derived from propylene in an amount of atleast about 60, preferably at least about 70 and more preferably atleast about 80, wt % of the polymer. The one or more unsaturatedcomonomers of the polymer comprise at least about 0.1, preferably atleast about 1 and more preferably at least about 3, weight percent, andthe typical maximum amount of unsaturated comonomer does not exceedabout 40, and preferably it does not exceed about 30, wt % of thepolymer.

The P/E* polymers are the preferred impact modifying polymers used inthe practice of this invention.

Molecular Weight

The weight average molecular weight (Mw) of the impact modifyingpolymers of this invention can vary widely, but typically it is betweenabout 50,000 and 200,000 (with the understanding that the only limit onthe minimum or the maximum M_(w) is that set by practicalconsiderations). “Low molecular weight”, “low weight average molecularweight”, “low Mw” and similar terms mean a weight average molecularweight of less than about 200,000, more preferably less than about175,000 and even more preferably less than about 150,000.

Polydispersity

The polydispersity of the impact modifying polymers is typically betweenabout 2 and about 6. “Narrow polydisperity”, “narrow molecular weightdistribution”, “narrow MWD” and similar terms mean a ratio (M_(w)/M_(n))of weight average molecular weight (M_(w)) to number average molecularweight (M_(n)) of less than about 3.5, typically less than about 3.0.

Impact modifying polymer blends may have a higher polydispersity,depending on the molecular weight of the various components of theblend. In particular, blends produced by any of a number of differentmultiple reactor processes may have a broad range of polydispersities,from as low as about 2 to as high as 100 or more. Preferably, theM_(w)/M_(n) of such blends is between about 2 and about 50, morepreferably between about 2 and about 20, most preferably between about 2and about 10.

Gel Permeation Chromatography

Molecular weight distribution of the polymers is determined using gelpermeation chromatography (GPC) on a Polymer Laboratories PL-GPC-220high temperature chromatographic unit equipped with four linear mixedbed columns (Polymer Laboratories (20-micron particle size)). The oventemperature is at 160° C. with the autosampler hot zone at 160° C. andthe warm zone at 145° C. The solvent is 1,2,4-trichlorobenzenecontaining 200 ppm 2,6-di-t-butyl-4-methylphenol. The flow rate is 1.0milliliter/minute and the injection size is 100 microliters. About 0.2%by weight solutions of the samples are prepared for injection bydissolving the sample in nitrogen purged 1,2,4-trichlorobenzenecontaining 200 ppm 2,6-di-t-butyl-4-methylphenol for 2.5 hrs at 160° C.with gentle mixing.

The molecular weight determination is deduced by using ten narrowmolecular weight distribution polystyrene standards (from PolymerLaboratories, EasiCal PSI ranging from 580-7,500,000 g/mole) inconjunction with their elution volumes. The equivalent polypropylenemolecular weights are determined by using appropriate Mark-Houwinkcoefficients for polypropylene (as described by Th. G. Scholte, N. L. J.Meijerink, H. M. Schoffeleers, and A. M. G. Brands, J. Appl. Polym.Sci., 29, 3763-3782 (1984)) and polystyrene (as described by E. P.Otocka, R. J. Roe, N. Y. Hellman, P. M. Muglia, Macromolecules, 4, 507(1971)) in the Mark-Houwink equation:{N}=KM^(a)where K_(pp)=1.90E-04, a_(pp)=0.725 and K_(ps)=1.26E-04, a_(ps)=0.702.Differential Scanning Calorimetry

Differential scanning calorimetry (DSC) is a common technique that canbe used to examine the melting and crystallization of semi-crystallinepolymers. General principles of DSC measurements and applications of DSCto studying semi-crystalline polymers are described in standard texts(e.g., E. A. Turi, ed., Thermal Characterization of Polymeric Materials,Academic Press, 1981). Certain of the copolymers of this invention arecharacterized by a DSC curve with a T_(me) that remains essentially thesame and a T_(max) that decreases as the amount of unsaturated comonomerin the copolymer is increased. T_(me) means the temperature at which themelting ends. T_(max) means the peak melting temperature.

Differential Scanning Calorimetry (DSC) analysis is determined using amodel Q1000 DSC from TA Instruments, Inc. Calibration of the DSC is doneas follows. First, a baseline is obtained by running the DSC from −90°C. to 290° C. without any sample in the aluminum DSC pan. Then 7milligrams of a fresh indium sample is analyzed by heating the sample to180° C., cooling the sample to 140° C. at a cooling rate of 10° C./minfollowed by keeping the sample isothermally at 140° C. for 1 minute,followed by heating the sample from 140° C. to 180° C. at a heating rateof 10° C./min. The heat of fusion and the onset of melting of the indiumsample are determined and checked to be within 0.5° C. from 156.6° C.for the onset of melting and within 0.5 J/g from 28.71 J/g for the heatof fusion. Then deionized water is analyzed by cooling a small drop offresh sample in the DSC pan from 25° C. to −30° C. at a cooling rate of10° C./min. The sample is kept isothermally at −30° C. for 2 minutes andheated to 30° C. at a heating rate of 10° C./min. The onset of meltingis determined and checked to be within 0.5° C. from 0° C.

The polypropylene samples are pressed into a thin film at a temperatureof 190° C. About 5 to 8 mg of sample is weighed out and placed in theDSC pan. The lid is crimped on the pan to ensure a closed atmosphere.The sample pan is placed in the DSC cell and the heated at a high rateof about 100° C./min to a temperature of about 30° C. above the melttemperature. The sample is kept at this temperature for about 3 minutes.Then the sample is cooled at a rate of 10° C./min to −40° C., and keptisothermally at that temperature for 3 minutes. Consequently the sampleis heated at a rate of 10° C./min until complete melting. The resultingenthalpy curves are analyzed for peak melt temperature, onset and peakcrystallization temperatures, heat of fusion and heat ofcrystallization, T_(me), and any other DSC analyses of interest.

B-Value

“High B-value” and similar terms mean the ethylene units of a copolymerof propylene and ethylene, or a copolymer of propylene, ethylene and atleast one unsaturated comononomer, is distributed across the polymerchain in a nonrandom manner. B-values range from 0 to 2 with 1designating a perfectly random distribution of comonomer units. Thehigher the B-value, the more alternating the comonomer distribution inthe copolymer. The lower the B-value, the more blocky or clustered thecomonomer distribution in the copolymer. The high B-values of thepolymers of this invention are typically at least about 1.3, preferablyat least about 1.4, more preferably at least about 1.5 and mostpreferably at least about 1.7. The B-value is calculated as follows.

B is defined for a propylene/ethylene copolymer as:

$B = \frac{f_{({{EP} + {PE}})}}{2 \cdot F_{E} \cdot F_{P}}$where f(EP+PE)=the sum of the EP and PE diad fractions; and Fe andFp=the mole fraction of ethylene and propylene in the copolymer,respectively. B-values can be calculated for other copolymers in ananalogous manner by assignment of the respective copolymer diads. Forexample, calculation of the B-value for a propylene/1-octene copolymeruses the following equation:

$B = \frac{f_{({{OP} + {PO}})}}{2 \cdot F_{O} \cdot F_{P}}$

For propylene polymers made with a metallocene catalyst, the B-valuesare typically between 1.1 and 1.3. For propylene polymers made with aconstrained geometry catalyst, the B-values are typically between 0.9and 1.0. In contrast, the B-values of the P/E* polymers, typically madewith an activated nonmetallocene, metal-centered, heteroaryl ligandcatalyst, are above about 1.4, typcially between about 1.5 and about1.85. In turn, this means that for any P/E* copolymer, not only is thepropylene block length relatively short for a given percentage ofethylene but very little, if any, long sequences of 3 or more sequentialethylene insertions are present in the copolymer, unless the ethylenecontent of the polymer is very high. FIG. 1 and the data of thefollowing tables are illustrative. The catalysts are activatednonmetallocene, metal-centered, heteroaryl ligand catalysts, and thesemade polymers of this invention. The Catalyst E is a metallocenecatalyst, and it did not make the P/E* polymers. Interestingly, theB-values of the P/E* polymers remained high even for polymers withrelatively large amounts, e.g., >30 mole %, ethylene.

TABLE A B-Values of Selected Propylene Polymers Regio-errors Cryst.14–16 ppm (%) MFR Density Ethylene (mole %) Tmax (from No Description(g/10 min) (kg/dm 3#) (mol %) (average of two) B (° C.) Hf) Tg (° C.)A-1 P/E* via 25.8 0.8864 10.6 0.00 1.40 104.7 37.3 −20.9 Catalyst I A-2HPP via 1.9 0.8995 0.0 1.35 None 139.5 48.7 −6.9 Catalyst G A-3 P/E* via1.7 0.8740 11.8 0.24 1.67 63.3 24.4 −23.6 Catalyst G A-4 P/E* via 1.50.8703 12.9 0.32 1.66 57.7 21.9 −24.5 Catalyst G A-5 HPP via 2.5 0.90210.0 1.18 none 143.5 61.4 −6.0 Catalyst H A-6 P/E* via 1.9 0.8928 4.30.57 1.77 120.6 48.3 −13.8 Catalyst H A-7 P/E* via 2.2 0.8850 8.2 0.471.71 96.0 40.5 −19.3 Catalyst H A-8 P/E* via 2.3 0.8741 11.8 0.34 1.7967.9 27.4 −23.7 Catalyst H A-9 P/E* via 2 0.8648 15.8 0.24 1.67 53.710.5 −27.6 Catalyst H A-10 P/E* via 2.0 0.8581 18.6 0.18 1.70 none 2.6−29.9 Catalyst HCatalyst I isdimethyleamidoborane-bis-η⁵-(2-methyl-4-napthylinden-1-yl)zirconiumη⁴-1,4-dipheny-1,3-butadiene. HPP means polypropylene homopolymer.Catalysts G, H and I are illustrated in FIGS. 10G, 10H and 10I,respectively.

TABLE B B-Values of Selected Propylene/Ethylene Copolymers Regio-errorsEthylene 14–16 ppm (mole %) Tmax Cryst. (%) No. Description (mol %)(average of two) B (° C.) (from Hf) Tg (° C.) B-1 P/E* via 1.6 0.37 1.78138.2 53.9 −8.1 Catalyst H B-2 P/E* via 7.7 0.38 1.66 105.6 38.9 −18.5Catalyst H B-3 P/E* via 7.8 0.41 1.61 107.7 39.6 −18.2 Catalyst H B-4P/E* via 12.3 0.31 1.58 74.7 30.7 −22.5 Catalyst H B-5 P/E* via 14.80.21 1.67 90.6 31.2 −22.9 Catalyst H B-6 P/E* via 12.4 0.31 1.61 67.420.8 −26.8 Catalyst H B-7 P/E* via 14.7 0.30 1.60 78.1 19.9 −25.9Catalyst H B-8 P/E* via 33.7 0.00 1.67 none 0.0 −39.2 Catalyst H B-9P/E* via 31.3 0.00 1.67 none 0.0 −39.2 Catalyst H B-10 P/E* via 12.00.25 1.61 72.4 33.2 −22.8 Catalyst J B-11 P/E* via 8.9 0.37 1.63 91.440.1 −19.8 Catalyst J B-12 P/E* via 8.5 0.44 1.68 101.7 38.7 −20.0Catalyst J B-13 P/E* via 7.6 0.47 1.68 107.6 43.2 −18.8 Catalyst J B-14P/E* via 7.6 0.35 1.64 106.2 42.4 −18.5 Catalyst J B-15 P/E* via 8.60.33 1.64 104.4 41.0 −19.5 Catalyst J B-16 P/E* via 9.6 0.35 1.65 85.538.1 −20.6 Catalyst J B-17 P/E* via 8.6 0.37 1.63 104.1 41.8 −19.6Catalyst J B-18 P/E* via 8.6 0.34 1.62 90.8 40.8 −19.6 Catalyst J B-19P/E* via 8.6 0.40 1.58 93.3 41.9 −19.2 Catalyst J

Catalyst J is illustrated in FIG. 10J.

The processes used to produce the P/E* copolymers produce interpolymershaving a relatively broad melting point in a DSC heating curve. Whilenot wishing to be held to any particular theory of operation, it isbelieved that the high B values for the propylene/ethylene interpolymersused in the practice of this invention and the process for theirmanufacture lead to an ethylene distribution within the polymer chainsthat leads to a broad melting behavior. In FIGS. 2A and 2B, for example,a relatively narrow melting peak is observed for a propylene/ethylenecopolymer prepared using a metallocene as a comparative example(Comparative Example 1), while the melting peak for a similar copolymerof propylene and ethylene prepared according to the teachings hereinexhibits a broad melting point. Such broad melting behavior is useful inapplications requiring, for example, a relatively low heat sealinitiation temperature, or a broad hot tack and/or heat seal window.

Thermal Properties

FIGS. 3 and 4 further illustrate the thermal properties of the P/E*polymers. FIG. 3 illustrates that the P/E* polymers have a higher glasstransition temperaure (Tg) than do comparable metallocene-catalysedpropylene polymers at a equivalent crystallinity. This means that theP/E* copolymers are likely to exhibit better creep resistance thanconventional metallocene-catalyzed propylene copolymers. Moreover, theT_(max) data of Table A shows that the P/E* copolymers have a lowermelting point at the same crystallinity as a metallocene-catalyzedpropylene copolymer. This, in turn, means that the P/E* polymers arelikely to process better (e.g., require less heating) than conventionalmetallocene-catalyzed propylene polymers.

FIG. 4 illustrates that the P/E* polymers also have a lower Tg at anequivalent ethylene content than a similar propylene polymer made with aconstrained geometry catalyst (CGC) and this, in turn, means that theP/E* polymers are likely to exhibit better low temperature toughnessthan the CGC propylene polymers making the P/E* polymers attractivecandidates for food packaging applications.

Temperature-Rising Elution Fractionation

The determination of crystallizable sequence length distribution can beaccomplished on a preparative scale by temperature-rising elutionfractionation (TREF). The relative mass of individual fractions can beused as a basis for estimating a more continuous distribution. L. Wild,et al., Journal of Polymer Science: Polymer. Physics Ed., 20, 441(1982), scaled down the sample size and added a mass detector to producea continuous representation of the distribution as a function of elutiontemperature. This scaled down version, analytical temperature-risingelution fractionation (ATREF), is not concerned with the actualisolation of fractions, but with more accurately determining the weightdistribution of fractions.

While TREF was originally applied to copolymers of ethylene and higherα-olefins, it can also be used for the analysis of copolymers ofpropylene with ethylene (or higher α-olefins). The analysis ofcopolymers of propylene requires higher temperatures for the dissolutionand crystallization of pure, isotactic polypropylene, but most of thecopolymerization products of interest elute at similar temperatures asobserved for copolymers of ethylene. The following table is a summary ofconditions used for the analysis of copolymers of propylene. Except asnoted the conditions for TREF are consistent with those of Wild, et al.,ibid, and Hazlitt, Journal of Applied Polymer Science: Appl. Polym.Symp., 45, 25(1990).

TABLE C Parameters Used for TREF Parameter Explanation Column type andsize Stainless steel shot with 1.5 cc interstitial volume Mass detectorSingle beam infrared detector at 2920 cm⁻¹ Injection temperature 150° C.Temperature control device GC oven Solvent 1,2,4-trichlorobenzeneConcentration 0.1 to 0.3% (weight/weight) Cooling Rate 1 140° C. to 120°C. @ −6.0° C./min. Cooling Rate 2 120° C. to 44.5° C. @ −0.1° C./min.Cooling Rate 3 44.5° C. to 20° C. @ −0.3° C./min. Heating Rate 20° C. to140° C. @ 1.8° C./min. Data acquisition rate 12/min.

The data obtained from TREF are expressed as a normalized plot of weightfraction as a function of elution temperature. The separation mechanismis analogous to that of copolymers of ethylene, whereby the molarcontent of the crystallizable component (ethylene) is the primary factorthat determines the elution temperature. In the case of copolymers ofpropylene, it is the molar content of isotactic propylene units thatprimarily determines the elution temperature. FIG. 5 is a representationof the typical type of distribution one would expect for apropylene/ethylene copolymer made with a metallocene polymer and anexample of the current invention.

The shape of the metallocene curve in FIG. 5 is typical for ahomogeneous copolymer. The shape arises from the inherent, randomincorporation of comonomer. A prominent characteristic of the shape ofthe curve is the tailing at lower elution temperature compared to thesharpness or steepness of the curve at the higher elution temperatures.A statistic that reflects this type of assymetry is skewness. Equation 1mathematically represents the skewness index, S_(ix), as a measure ofthis asymmetry.

$\begin{matrix}{S_{ix} = {\frac{\sqrt[3]{\sum{w_{i}*( {T_{i} - T_{Max}} )^{3}}}}{\sum{w_{i}*( {T_{i} - T_{Max}} )^{2}}}.}} & {{Equation}\mspace{14mu} 1}\end{matrix}$

The value, T_(Max), is defined as the temperature of the largest weightfraction eluting between 50 and 90° C. in the TREF curve. T_(i) andw_(i) are the elution temperature and weight fraction respectively of anabitrary, i^(th) fraction in the TREF distribution. The distributionshave been normalized (the sum of the w_(i) equals 100%) with respect tothe total area of the curve eluting above 30° C. Thus, the indexreflects only the shape of the crystallized polymer and anyuncrystallized polymer (polymer still in solution at or below 30° C.)has been omitted from the calculation shown in Equation 1.

Polymer Definitions and Descriptions

“Polymer” means a macromolecular compound prepared by polymerizingmonomers of the same or different type. “Polymer” includes homopolymers,copolymers, terpolymers, interpolymers, and so on. The term“interpolymer” means a polymer prepared by the polymerization of atleast two types of monomers or comonomers. It includes, but is notlimited to, copolymers (which usually refers to polymers prepared fromtwo different types of monomers or comonomers, although it is often usedinterchangeably with “interpolymer” to refer to polymers made from threeor more different types of monomers or comonomers), terpolymers (whichusually refers to polymers prepared from three different types ofmonomers or comonomers), tetrapolymers (which usually refers to polymersprepared from four different types of monomers or comonomers), and thelike. The terms “monomer” or “comonomer” are used interchangeably, andthey refer to any compound with a polymerizable moiety which is added toa reactor in order to produce a polymer. In those instances in which apolymer is described as comprising one or more monomers, e.g., a polymercomprising propylene and ethylene, the polymer, of course, comprisesunits derived from the monomers, e.g., —CH₂—CH₂—, and not the monomeritself, e.g., CH₂═CH₂.

“Metallocene-catalyzed polymer” or similar term means any polymer thatis made in the presence of a metallocene catalyst. “Constrained geometrycatalyst catalyzed polymer”, “CGC-catalyzed polymer” or similar termmeans any polymer that is made in the presence of a constrained geometrycatalyst. “Ziegler-Natta-catalyzed polymer”, Z-N-catalyzed polymer” orsimilar term means any polymer that is made in the presence of aZiegler-Natta catalyst. “Metallocene” means a metal-containing compoundhaving at least one substituted or unsubstituted cyclopentadienyl groupbound to the metal. “Constrained geometry catalyst” or “CGC” as hereused has the same meaning as this term is defined and described in U.S.Pat. Nos. 5,272,236 and 5,278,272.

“Random copolymer” means a copolymer in which the monomer is randomlydistributed across the polymer chain.

“Impact copolymer”, “impact copolymer blend” and similar terms mean twoor more polymers in which one polymer is dispersed in the other polymer,typically one polymer comprising a matrix phase and the other polymercomprising an elastomer phase.

The unsaturated comonomers used in the practice of this inventioninclude, C₄₋₂₀ α-olefins, especially C₄₋₁₂ α-olefins such as 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene,1-dodecene and the like; C₄₋₂₀ diolefins, preferably 1,3-butadiene,1,3-pentadiene, norbornadiene, 5-ethylidene-2-norbornene (ENB) anddicyclopentadiene; C₈₋₄₀ vinyl aromatic compounds including sytrene, o-,m-, and p-methylstyrene, divinylbenzene, vinylbiphenyl, vinylnapthalene;and halogen-substituted C₈₋₄₀ vinyl aromatic compounds such aschlorostyrene and fluorostyrene. For purposes of this invention,ethylene and propylene are not included in the definition of unsaturatedcomonomers.

The propylene/ethylene impact modifiers of this invention typicallycomprise units derived from propylene in an amount of at least about 60,preferably at least about 80 and more preferably at least about 85, wt %of the copolymer. The typical amount of units derived from ethylene inpropylene/ethylene copolymers is at least about 0.1, preferably at leastabout 1 and more preferably at least about 5 wt %, and the maximumamount of units derived from ethylene present in these copolymers istypically not in excess of about 35, preferably not in excess of about30 and more preferably not in excess of about 20, wt % of the copolymer.The amount of units derived from the unsaturated comonomer(s), ifpresent, is typically at least about 0.01, preferably at least about 1and more preferably at least about 5, wt %, and the typical maximumamount of units derived from the unsaturated comonomer(s) typically doesnot exceed about 35, preferably it does not exceed about 30 and morepreferably it does not exceed about 20, wt % of the copolymer. Thecombined total of units derived from ethylene and any unsaturatedcomonomer typically does not exceed about 40, preferably it does notexceed about 30 and more preferably it does not exceed about 20, wt % ofthe copolymer.

The propylene/unsaturated comonomer impact modifiers of this inventioncomprising propylene and one or more unsaturated comonomers (other thanethylene) also typically comprise units derived from propylene in anamount of at least about 60, preferably at least about 70 and morepreferably at least about 80, wt % of the copolymer. The one or moreunsaturated comonomers of the copolymer comprise at least about 0.1,preferably at least about 1 and more preferably at least about 3, weightpercent, and the typical maximum amount of unsaturated comonomer doesnot exceed about 40, and preferably it does not exceed about 30, wt % ofthe copolymer.

¹³C NMR

The P* and P/E* polymers are further characterized as havingsubstantially isotactic propylene sequences. “Substantially isotacticpropylene sequences” and similar terms mean that the sequences have anisotactic triad (mm) measured by ¹³C NMR of greater than about 0.85,preferably greater than about 0.90, more preferably greater than about0.92 and most preferably greater than about 0.93. Isotactic triads arewell known in the art and are described in, for example, U.S. Pat. No.5,504,172 and WO 00/01745 which refer to the isotactic sequence in termsof a triad unit in the copolymer molecular chain determined by ¹³C NMRspectra. NMR spectra are determined as follows.

¹³C NMR spectroscopy is one of a number of techniques known in the artof measuring comonomer incorporation into a polymer. An example of thistechnique is described for the determination of comonomer content forethylene/α-olefin copolymers in Randall (Journal of MacromolecularScience, Reviews in Macromolecular Chemistry and Physics, C29 (2 & 3),201-317 (1989)). The basic procedure for determining the comonomercontent of an olefin interpolymer involves obtaining the ¹³C NMRspectrum under conditions where the intensity of the peaks correspondingto the different carbons in the sample is directly proportional to thetotal number of contributing nuclei in the sample. Methods for ensuringthis proportionality are known in the art and involve allowance forsufficient time for relaxation after a pulse, the use ofgated-decoupling techniques, relaxation agents, and the like. Therelative intensity of a peak or group of peaks is obtained in practicefrom its computer-generated integral. After obtaining the spectrum andintegrating the peaks, those peaks associated with the comonomer areassigned. This assignment can be made by reference to known spectra orliterature, or by synthesis and analysis of model compounds, or by theuse of isotopically labeled comonomer. The mole % comonomer can bedetermined by the ratio of the integrals corresponding to the number ofmoles of comonomer to the integrals corresponding to the number of molesof all of the monomers in the interpolymer, as described in Randall, forexample.

The data is collected using a Varian UNITY Plus 400 MHz NMRspectrometer, corresponding to a ¹³C resonance frequency of 100.4 MHz.Acquisition parameters are selected to ensure quantitative ¹³C dataacquisition in the presence of the relaxation agent. The data isacquired using gated ¹H decoupling, 4000 transients per data file, a 7sec pulse repetition delay, spectral width of 24,200 Hz and a file sizeof 32K data points, with the probe head heated to 130° C. The sample isprepared by adding approximately 3 mL of a 50/50 mixture oftetrachloroethane-d2/orthodichlorobenzene that is 0.025M in chromiumacetylacetonate (relaxation agent) to 0.4 g sample in a 10 mm NMR tube.The headspace of the tube is purged of oxygen by displacement with purenitrogen. The sample is dissolved and homogenized by heating the tubeand its contents to 150° C. with periodic refluxing initiated by heatgun.

Following data collection, the chemical shifts are internally referencedto the mmmm pentad at 21.90 ppm.

For propylene/ethylene copolymers, the following procedure is used tocalculate the percent ethylene in the polymer. Integral regions aredetermined as follows:

TABLE D Integral Regions for Determining % Ethylene Region designationppm A 44–49 B 36–39 C 32.8–34   P 31.0–30.8 Q Peak at 30.4 R Peak at 30F 28.0–29.7 G   26–28.3 H 24–26 I 19–23Region D is calculated as D=P×(G×Q)/2. Region E=R+Q+(G×Q)/2.

TABLE E Calculation of Region D PPP = (F + A − 0.5 D)/2 PPE = D EPE = CEEE = (E − 0.5 G)/2 PEE = G PEP = H Moles P = sum P centered triadsMoles E = sum E centered triads Moles P = (B + 2A)/2 Moles E = (E + G +0.5B + H)/2

C2 values are calculated as the average of the two methods above (triadsummation and algebraic) although the two do not usually vary.

The mole fraction of propylene insertions resulting in regio-errors iscalculated as one half of the sum of the two of methyls showing up at14.6 and 15.7 ppm divided by the total methyls at 14-22 ppm attributableto propylene. The mole percent of the regio-error peaks is the molefraction times 100.

Isotacticity at the triad level (mm) is determined from the integrals ofthe mm triad (22.70-21.28 ppm), the mr triad (21.28-20.67 ppm) and therr triad (20.67-19.74). The mm isotacticity is determined by dividingthe intensity of the mm triad by the sum of the mm, mr, and rr triads.For ethylene copolymers the mr region is corrected by subtracting37.5-39 ppm integral. For copolymers with other monomers that producepeaks in the regions of the mm, mr, and rr triads, the integrals forthese regions are similarly corrected by subtracting the intensity ofthe interfering peak using standard NMR techniques, once the peaks havebeen identified. This can be accomplished, for example, by analysis of aseries of copolymers of various levels of monomer incorporation, byliterature assignments, by isotopic labeling, or other means which areknown in the art.

The ¹³C NMR peaks corresponding to a regio-error at about 14.6 and about15.7 ppm are believed to be the result of stereoselective 2,1-insertionerrors of propylene units into the growing polymer chain. In a typicalpolymer of this invention, these peaks are of about equal intensity, andthey represent about 0.02 to about 7 mole percent of the propyleneinsertions into the homopolymer or copolymer chain. For some embodimentsof this invention, they represent about 0.005 to about 20 mole % or moreof the propylene insertions. In general, higher levels of regio-errorslead to a lowering of the melting point and the modulus of the polymer,while lower levels lead to a higher melting point and a higher modulusof the polymer.

The nature and level of comonomers other than propylene present in thecopolymer also control the melting point and modulus of the copolymer.In any particular application, it may be desirable to have either a highor low melting point or a high or low modulus modulus. The level ofregio-errors can be controlled by several means, including thepolymerization temperature, the concentration of propylene and othermonomers in the process, the type of (co)monomers, and other factors.Various individual catalyst structures may inherently produce more orless regio-errors than other catalysts. For example, in Table A above,the propylene homopolymer prepared with Catalyst G has a higher level ofregio-errors and a lower melting point than the propylene homopolymerprepared with Catalyst H, which has a higher melting point. If a highermelting point (or higher modulus) polymer is desired, then it ispreferable to have fewer regio-errors than about 3 mole % of thepropylene insertions, more preferably less than about 1.5 mole % of thepropylene insertions, still more preferably less than about 1.0 mole %of the propylene insertions, and most preferably less than about 0.5mole % of the propylene insertions. If a lower melting point (ormodulus) polymer is desired, then it is preferable to have moreregio-errors than about 3 mole % of the propylene insertions, morepreferably more than about 5 mole % of the propylene insertions, stillmore preferably more than about 6 mole % of the propylene insertions,and most preferably more than about 10 mole % of the propyleneinsertions.

Those skilled artisan will appreciate that the mole % of regio-errorsfor a P/E* polymer which is a component of a blend refers to the mole %of regio-errors of the particular P/E* polymer component of the blend,and not as a mole % of the overall blend.

The comparison of several ¹³C NMR sprectra further illustrates theunique regio-errors of the P/E* polymers used in the practice of thisinvention. FIGS. 6 and 7 are the spectra of the propylene homopolymerproducts of Examples 7 and 8, respectively, each made with an activatednonmetallocene, metal-centered, heteroaryl ligand catalyst. The spectrumof each polymer reports a high degree of isotacticity and the uniqueregio-errors of these P/E* polymers. FIG. 8 is the ¹³C NMR spectrum ofthe propylene-ethylene copolymer of Example 2, made with the samecatalyst used to make the propylene homopolymer of Example 7, and it tooreports a high degree of isotacticity and the same regio-errors of thepropylene homopolymers of FIGS. 6 and 7. The presence of the ethylenecomonomer does not preclude the occurrence of these unique regio-errors.The ¹³C NMR spectrum of FIG. 9 is that of the propylene-ethylenecopolymer product of Comparative Example 1 which was prepared using ametallocene catalyst. This spectrum does not report the regio-error(around 15 ppm) characteristic of the P/E* polymers used in the practiceof this invention.

Melt Flow Rate

The impact modifying copolymers of this invention typically have an MFRof at least about 0.01, preferably at least about 0.05, more preferablyat least about 0.1 and most preferably at least about 0.2. The maximumMFR typically does not exceed about 1,000, preferably it does not exceedabout 500, more preferably it does not exceed about 100, more preferablyit does not exceed about 80 and most preferably it does not exceed about50. The MFR for propylene homopolymers and copolymers of propylene andethylene and/or one or more C₄-C₂₀ α-olefins is measured according toASTM D-1238, condition L (2.16 kg, 230 degrees C.).

Propylene Copolymers

The impact modifying copolymers of this invention include propylenecopolymers and terpolymers, sometimes referred to as propylene orpropylene-based rubbers. The terpolymers are usually preferred to thecopolymers if good optics, i.e., clarity, is an important feature of thematix/rubber blend. Of particular interest are copolymers andterpolymers of propylene/ethylene, propylene/1-butene,propylene/1-hexene, propylene/4-methyl-1-pentene, propylene/1-octene,propylene/ethylene/1-butene, propylene/ethylene/ENB,propylene/ethylene/1-hexene, propylene/ethylene/1-octene,propylene/styrene, and propylene/ethylene/styrene.

Catalyst Definitions and Descriptions

The P* and P/E* polymers used in the practice of this invention are madeusing a metal-centered, heteroaryl ligand catalyst in combination withone or more activators, e.g., an alumoxane. In certain embodiments, themetal is one or more of hafnium and zirconium.

More specifically, in certain embodiments of the catalyst, the use of ahafnium metal has been found to be preferred as compared to a zirconiummetal for heteroaryl ligand catalysts. A broad range of ancillary ligandsubstituents may accommodate the enhanced catalytic performance. Thecatalysts in certain embodiments are compositions comprising the ligandand metal precursor, and, optionally, may additionally include anactivator, combination of activators or activator package.

The catalysts used to make the P* and P/E* polymers used in the practiceof this invention additionally include catalysts comprising ancillaryligand-hafnium complexes, ancillary ligand-zirconium complexes andoptionally activators, which catalyze polymerization andcopolymerization reactions, particularly with monomers that are olefins,diolefins or other unsaturated compounds. Zirconium complexes, hafniumcomplexes, compositions or compounds using the disclosed ligands arewithin the scope of the catalysts useful in the practice of thisinvention. The metal-ligand complexes may be in a neutral or chargedstate. The ligand to metal ratio may also vary, the exact ratio beingdependent on the nature of the ligand and metal-ligand complex. Themetal-ligand complex or complexes may take different forms, for example,they may be monomeric, dimeric or of an even higher order.

“Nonmetallocene, metal-centered, heteroaryl ligand catalyst” means thecatalyst derived from the ligand described in formula I. As used in thisphrase, “heteroaryl” includes substituted heteroaryl.

As used herein, the phrase “characterized by the formula” is notintended to be limiting and is used in the same way that “comprising” iscommonly used. The term “independently selected” is used herein toindicate that the R groups, e.g., R¹, R², R³, R⁴, and R⁵ can beidentical or different (e.g. R¹, R², R³, R⁴, and R⁵ may all besubstituted alkyls or R¹ and R² may be a substituted alkyl and R³ may bean aryl, etc.). Use of the singular includes use of the plural and viceversa (e.g., a hexane solvent, includes hexanes). A named R group willgenerally have the structure that is recognized in the art ascorresponding to R groups having that name. The terms “compound” and“complex” are generally used interchangeably in this specification, butthose of skill in the art may recognize certain compounds as complexesand vice versa. For the purposes of illustration, representative certaingroups are defined herein. These definitions are intended to supplementand illustrate, not preclude, the definitions known to those of skill inthe art.

“Hydrocarbyl” refers to univalent hydrocarbyl radicals containing 1 toabout 30 carbon atoms, preferably 1 to about 24 carbon atoms, mostpreferably 1 to about 12 carbon atoms, including branched or unbranched,saturated or unsaturated species, such as alkyl groups, alkenyl groups,aryl groups, and the like. “Substituted hydrocarbyl” refers tohydrocarbyl substituted with one or more substituent groups, and theterms “heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” referto hydrocarbyl in which at least one carbon atom is replaced with aheteroatom.

The term “alkyl” is used herein to refer to a branched or unbranched,saturated or unsaturated acyclic hydrocarbon radical. Suitable alkylradicals include, for example, methyl, ethyl, n-propyl, i-propyl,2-propenyl (or allyl), vinyl, n-butyl, t-butyl, i-butyl (or2-methylpropyl), etc. In particular embodiments, alkyls have between 1and 200 carbon atoms, between 1 and 50 carbon atoms or between 1 and 20carbon atoms.

“Substituted alkyl” refers to an alkyl as just described in which one ormore hydrogen atom bound to any carbon of the alkyl is replaced byanother group such as a halogen, aryl, substituted aryl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,halogen, alkylhalos (e.g., CF₃), hydroxy, amino, phosphido, alkoxy,amino, thio, nitro, and combinations thereof. Suitable substitutedalkyls include, for example, benzyl, trifluoromethyl and the like.

The term “heteroalkyl” refers to an alkyl as described above in whichone or more carbon atoms to any carbon of the alkyl is replaced by aheteroatom selected from the group consisting of N, O, P, B, S, Si, Sb,Al, Sn, As, Se and Ge. This same list of heteroatoms is usefulthroughout this specification. The bond between the carbon atom and theheteroatom may be saturated or unsaturated. Thus, an alkyl substitutedwith a heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, or seleno is within the scope of the term heteroalkyl. Suitableheteroalkyls include cyano, benzoyl, 2-pyridyl, 2-furyl and the like.

The term “cycloalkyl” is used herein to refer to a saturated orunsaturated cyclic non-aromatic hydrocarbon radical having a single ringor multiple condensed rings. Suitable cycloalkyl radicals include, forexample, cyclopentyl, cyclohexyl, cyclooctenyl, bicyclooctyl, etc. Inparticular embodiments, cycloalkyls have between 3 and 200 carbon atoms,between 3 and 50 carbon atoms or between 3 and 20 carbon atoms.

“Substituted cycloalkyl” refers to cycloalkyl as just describedincluding in which one or more hydrogen atom to any carbon of thecycloalkyl is replaced by another group such as a halogen, alkyl,substituted alkyl, aryl, substituted aryl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, seleno and combinations thereof. Suitable substituted cycloalkylradicals include, for example, 4-dimethylaminocyclohexyl,4,5-dibromocyclohept-4-enyl, and the like.

The term “heterocycloalkyl” is used herein to refer to a cycloalkylradical as described, but in which one or more or all carbon atoms ofthe saturated or unsaturated cyclic radical are replaced by a heteroatomsuch as nitrogen, phosphorous, oxygen, sulfur, silicon, germanium,selenium, or boron. Suitable heterocycloalkyls include, for example,piperazinyl, morpholinyl, tetrahydropyranyl, tetrahydrofuranyl,piperidinyl, pyrrolidinyl, oxazolinyl and the like.

“Substituted heterocycloalkyl” refers to heterocycloalkyl as justdescribed including in which one or more hydrogen atom to any atom ofthe heterocycloalkyl is replaced by another group such as a halogen,alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, seleno and combinations thereof. Suitable substitutedheterocycloalkyl radicals include, for example, N-methylpiperazinyl,3-dimethylaminomorpholinyl and the like.

The term “aryl” is used herein to refer to an aromatic substituent whichmay be a single aromatic ring or multiple aromatic rings which are fusedtogether, linked covalently, or linked to a common group such as amethylene or ethylene moiety. The aromatic ring(s) may include phenyl,naphthyl, anthracenyl, and biphenyl, among others. In particularembodiments, aryls have between 1 and 200 carbon atoms, between 1 and 50carbon atoms or between 1 and 20 carbon atoms.

“Substituted aryl” refers to aryl as just described in which one or morehydrogen atom bound to any carbon is replaced by one or more functionalgroups such as alkyl, substituted alkyl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen,alkylhalos (e.g., CF₃), hydroxy, amino, phosphido, alkoxy, amino, thio,nitro, and both saturated and unsaturated cyclic hydrocarbons which arefused to the aromatic ring(s), linked covalently or linked to a commongroup such as a methylene or ethylene moiety. The common linking groupmay also be a carbonyl as in benzophenone or oxygen as in diphenyletheror nitrogen in diphenylamine.

The term “heteroaryl” as used herein refers to aromatic or unsaturatedrings in which one or more carbon atoms of the aromatic ring(s) arereplaced by a heteroatom(s) such as nitrogen, oxygen, boron, selenium,phosphorus, silicon or sulfur. Heteroaryl refers to structures that maybe a single aromatic ring, multiple aromatic ring(s), or one or morearomatic rings coupled to one or more non-aromatic ring(s). Instructures having multiple rings, the rings can be fused together,linked covalently, or linked to a common group such as a methylene orethylene moiety. The common linking group may also be a carbonyl as inphenyl pyridyl ketone. As used herein, rings such as thiophene,pyridine, isoxazole, pyrazole, pyrrole, furan, etc. or benzo-fusedanalogues of these rings are defined by the term “heteroaryl.”

“Substituted heteroaryl” refers to heteroaryl as just describedincluding in which one or more hydrogen atoms bound to any atom of theheteroaryl moiety is replaced by another group such as a halogen, alkyl,substituted alkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio,seleno and combinations thereof. Suitable substituted heteroarylradicals include, for example, 4-N,N-dimethylaminopyridine.

The term “alkoxy” is used herein to refer to the —OZ¹ radical, where Z¹is selected from the group consisting of alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heterocylcoalkyl, substitutedheterocycloalkyl, silyl groups and combinations thereof as describedherein. Suitable alkoxy radicals include, for example, methoxy, ethoxy,benzyloxy, t-butoxy, etc. A related term is “aryloxy” where Z¹ isselected from the group consisting of aryl, substituted aryl,heteroaryl, substituted heteroaryl, and combinations thereof. Examplesof suitable aryloxy radicals include phenoxy, substituted phenoxy,2-pyridinoxy, 8-quinalinoxy and the like.

As used herein the term “silyl” refers to the —SiZ¹Z²Z³ radical, whereeach of Z¹, Z², and Z³ is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, amino, silyl and combinationsthereof.

As used herein the term “boryl” refers to the —BZ¹Z² group, where eachof Z¹ and Z² is independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, heterocycloalkyl,heterocyclic, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, amino, silyl and combinations thereof.

As used herein, the term “phosphino” refers to the group —PZ¹Z², whereeach of Z¹ and Z² is independently selected from the group consisting ofhydrogen, substituted or unsubstituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,silyl, alkoxy, aryloxy, amino and combinations thereof.

As used herein, the term “phosphine” refers to the group: PZ¹Z²Z³, whereeach of Z¹, Z³ and Z² is independently selected from the groupconsisting of hydrogen, substituted or unsubstituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,silyl, alkoxy, aryloxy, amino and combinations thereof.

The term “amino” is used herein to refer to the group —NZ¹Z², where eachof Z¹ and Z² is independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl andcombinations thereof.

The term “amine” is used herein to refer to the group: NZ¹Z²Z³, whereeach of Z¹, Z² and Z² is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl (including pyridines), substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

The term “thio” is used herein to refer to the group —SZ¹, where Z¹ isselected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

The term “seleno” is used herein to refer to the group —SeZ¹, where Z¹is selected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

The term “saturated” refers to lack of double and triple bonds betweenatoms of a radical group such as ethyl, cyclohexyl, pyrrolidinyl, andthe like.

The term “unsaturated” refers to the presence one or more double and/ortriple bonds between atoms of a radical group such as vinyl, acetylide,oxazolinyl, cyclohexenyl, acetyl and the like.

Ligands

Suitable ligands useful in the catalysts can be characterized broadly asmonoanionic ligands having an amine and a heteroaryl or substitutedheteroaryl group. The ligands of the catalysts are referred to, for thepurposes of this disclosure, as nonmetallocene ligands, and may becharacterized by the following general formula:

wherein R¹ is very generally selected from the group consisting ofalkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl and combinations thereof. In many embodiments, R¹ is a ringhaving from 4-8 atoms in the ring generally selected from the groupconsisting of substituted cycloalkyl, substituted heterocycloalkyl,substituted aryl and substituted heteroaryl, such that R¹ may becharacterized by the general formula:

where Q¹ and Q⁵ are substituents on the ring ortho to atom E, with Ebeing selected from the group consisting of carbon and nitrogen and withat least one of Q¹ or Q⁵ being bulky (defined as having at least 2atoms). Q¹ and Q⁵ are independently selected from the group consistingof alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl,substituted aryl and silyl, but provided that Q¹ and Q⁵ are not bothmethyl. Q″_(q) represents additional possible substituents on the ring,with q being 1, 2, 3, 4 or 5 and Q″ being selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof.T is a bridging group selected group consisting of —CR²R³— and —SiR²R³—with R² and R³ being independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio,seleno, halide, nitro, and combinations thereof. J″ is generallyselected from the group consisting of heteroaryl and substitutedheteroaryl, with particular embodiments for particular reactions beingdescribed herein.

In a more specific embodiment, suitable nonmetallocene ligands may becharacterized by the following general formula:

wherein R¹ and T are as defined above and each of R⁴, R⁵, R⁶ and R⁷ isindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl,aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro,and combinations thereof. Optionally, any combination of R¹, R², R³ andR⁴ may be joined together in a ring structure.

In certain more specific embodiments, the ligands may be characterizedby the following general formula:

wherein Q¹, Q⁵, R², R³, R⁴, R⁵, R⁶and R⁷ are as defined above. Q², Q³and Q⁴ are independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio,seleno, nitro, and combinations thereof.

In other more specific embodiments, the ligands may be characterized bythe following general formula:

wherein R¹, R², R³, R⁴, R⁵, and R⁶ are as defined above. In thisembodiment the R⁷ substituent has been replaced with an aryl orsubstituted aryl group, with R¹⁰, R¹¹, R¹² and R¹³ being independentlyselected from the group consisting of hydrogen, halo, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinationsthereof; optionally, two or more R¹⁰, R¹¹, R¹² and R¹³ groups may bejoined to form a fused ring system having from 3-50 non-hydrogen atoms.R¹⁴ is selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro,and combinations thereof.

In still more specific embodiments, the ligands may be characterized bythe general formula:

wherein R²-R⁶, R¹⁰-R¹⁴ and Q¹-Q⁵ are all as defined above.

In certain embodiments, R² is preferably hydrogen. Also preferably, eachof R⁴ and R⁵ is hydrogen and R⁶ is either hydrogen or is joined to R⁷ toform a fused ring system. Also preferred is where R³ is selected fromthe group consisting of benzyl, phenyl, 2-biphenyl, t-butyl,2-dimethylaminophenyl (2-(NMe₂)-C₆H₄—), 2-methoxyphenyl (2-MeO—C₆H₄—),anthracenyl, mesityl, 2-pyridyl, 3,5-dimethylphenyl, o-tolyl,9-phenanthrenyl. Also preferred is where R¹ is selected from the groupconsisting of mesityl, 4-isopropylphenyl (4-Pr^(i)-C₆H₄—), napthyl,3,5-(CF₃)₂—C₆H₃—, 2-Me-napthyl, 2,6-(Pr^(i))₂-C₆H₃—, 2-biphenyl,2-Me-4-MeO—C₆H₃—; 2-Bu^(t)-C₆H₄—, 2,5-(Bu^(t))₂-C₆H₃—,2-Pr^(i)-6-Me-C₆H₃—; 2-Bu^(t)-6-Me-C₆H₃—, 2,6-Et₂-C₆H₃—,2-sec-butyl-6-Et-C₆H₃— Also preferred is where R⁷ is selected from thegroup consisting of hydrogen, phenyl, napthyl, methyl, anthracenyl,9-phenanthrenyl, mesityl, 3,5-(CF₃)₂—C₆H₃—, 2-CF₃—C₆H₄—, 4-CF₃—C₆H₄—,3,5-F₂—C₆H₃—, 4-F—C₆H₃—, 2,4-F₂—C₆H₃—, 4-(NMe₂)-C₆H₄—, 3-MeO—C₆H₄—,4-MeO—C₆H₄—, 3,5-Me₂-C₆H₃—, o-tolyl, 2,6-F₂—C₆H₃— or where R⁷ is joinedtogether with R⁶ to form a fused ring system, e.g., quinoline.

Also optionally, two or more R⁴, R⁵, R⁶, R⁷ groups may be joined to forma fused ring system having from 3-50 non-hydrogen atoms in addition tothe pyridine ring, e.g. generating a quinoline group. In theseembodiments, R³ is selected from the group consisting of aryl,substituted aryl, heteroaryl, substituted heteroaryl, primary andsecondary alkyl groups, and —PY₂ where Y is selected from the groupconsisting of aryl, substituted aryl, heteroaryl, and substitutedheteroaryl.

Optionally within above formulas IV and V, R⁶ and R¹⁰ may be joined toform a ring system having from 5-50 non-hydrogen atoms. For example, ifR⁶ and R¹⁰ together form a methylene, the ring will have 5 atoms in thebackbone of the ring, which may or may not be substituted with otheratoms. Also for example, if R⁶ and R¹⁰ together form an ethylene, thering will have 6 atoms in the backbone of the ring, which may or may notbe substituted with other atoms. Substituents from the ring can beselected from the group consisting of halo, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinationsthereof.

In certain embodiments, the ligands are novel compounds. One example ofthe novel ligand compounds, includes those compounds generallycharacterized by formula (III), above where R² is selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, aryl, and substituted aryl; and R³ is aphosphino characterized by the formula —PZ¹Z², where each of Z¹ and Z²is independently selected from the group consisting of hydrogen,substituted or unsubstituted alkyl, cycloalkyl, heterocycloalkyl,heterocyclic, aryl, substituted aryl, heteroaryl, silyl, alkoxy,aryloxy, amino and combinations thereof. Particularly preferredembodiments of these compounds include those where Z¹ and Z² are eachindependently selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, heterocycloalkyl, aryl, and substituted aryl; andmore specifically phenyl; where Q¹, Q³, and Q⁵ are each selected fromthe group consisting of alkyl and substituted alkyl and each of Q² andQ⁴ is hydrogen; and where R⁴, R⁵, R⁶ and R⁷ are each hydrogen.

The ligands of the catalysts used to prepare the P/E* polymers used inthe practice of this invention may be prepared using known procedures.See, for example, Advanced Organic Chemistry, March, Wiley, New York1992 (4^(th) Ed.). Specifically, the ligands may be prepared using thetwo step procedure outlined in Scheme 1.

In Scheme 1, the * represents a chiral center when R² and R³ are notidentical; also, the R groups have the same definitions as above.Generally, R³M² is a nucleophile such as an alkylating or arylating orhydrogenating reagent and M² is a metal such as a main group metal, or ametalloid such as boron. The alkylating, arylating or hydrogenatingreagent may be a Grignard, alkyl, aryl-lithium or borohydride reagent.Scheme 1, step 2 first employs the use of complexing reagent.Preferably, as in the case of Scheme 1, magnesium bromide is used as thecomplexing reagent. The role of the complexing reagent is to direct thenucleophile, R³M², selectively to the imine carbon. Where the presenceof functional groups impede this synthetic approach, alternativesynthetic strategies may be employed. For instance, ligands whereR³=phosphino can be prepared in accordance with the teachings of U.S.Pat. Nos. 6,034,240 and 6,043,363. In addition, tetra-alkylhafniumcompounds or tetra-substituted alkylhafnium compounds ortetra-arylhafnium compounds or tetra-substituted arylhafnium compoundsmay be employed in step 2, in accordance with the teachings of U.S. Pat.No. 6,103,657. Scheme 2 further describes a synthesis process:

In scheme 2, h=1 or 2 and the bromine ions may or may not be bound tothe magnesium. The effect of the complexation is to guide the subsequentnucleophilic attack by R³M² to the imine carbon. As shown in Scheme 2 bythe *, where R² and R³ are different, this approach also leads to theformation of a chiral center on the ancillary ligands. For P* and P/E*polymers, this chiral center is important to the tacitity of thepolymers. Under some circumstances R³M² may be successfully added to theimine in the absence the complexing reagent. Ancillary ligands thatpossess chirality may be important in certain olefin polymerizationreactions, particularly those that lead to a stereospecific polymer, see“Stereospecific Olefin Polymerization with Chiral MetalloceneCatalysts”, Brintzinger, et al., Angew. Chem. Int. Ed. Engl., 1995, Vol.34, pp. 1143-1170, and the references therein; Bercaw et al., J. Am.Chem. Soc., 1999, Vol. 121, 564-573; and Bercaw et al., J. Am. Chem.Soc., 1996, Vol. 118, 11988-11989.

Compositions

Once the desired ligand is formed, it may be combined with a metal atom,ion, compound or other metal precursor compound. In some applications,the ligands of this invention will be combined with a metal compound orprecursor and the product of such combination is not determined, if aproduct forms. For example, the ligand may be added to a reaction vesselat the same time as the metal or metal precursor compound along with thereactants, activators, scavengers, etc. Additionally, the ligand can bemodified prior to addition to or after the addition of the metalprecursor, e.g. through a deprotonation reaction or some othermodification.

For formulas I, II, III, IV and V, the metal precursor compounds may becharacterized by the general formula Hf(L)_(n) where L is independentlyselected from the group consisting of halide (F, Cl, Br, I), alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene,seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates,oxalates, carbonates, nitrates, sulphates, and combinations thereof. nis 1, 2, 3, 4, 5, or 6. The hafnium precursors may be monomeric, dimericor higher orders thereof. It is well known that hafnium metal typicallycontains some amount of impurity of zirconium. Thus, this invention usesas pure hafnium as is commercially reasonable. Specific examples ofsuitable hafnium precursors include, but are not limited to HfCl₄,Hf(CH₂Ph)₄, Hf(CH₂CMe₃)₄, Hf(CH₂SiMe₃)₄, Hf(CH₂Ph)₃Cl, Hf(CH₂CMe₃)₃Cl,Hf(CH₂SiMe₃)₃Cl, Hf(CH₂Ph)₂Cl₂, Hf(CH₂CMe₃)₂Cl₂, Hf(CH₂SiMe₃)₂Cl₂,Hf(NMe₂)₄, Hf(NEt₂)₄, and Hf(N(SiMe₃)₂)₂Cl₂. Lewis base adducts of theseexamples are also suitable as hafnium precursors, for example, ethers,amines, thioethers, phosphines and the like are suitable as Lewis bases.

For formulas IV and V, the metal precursor compounds may becharacterized by the general formula M(L)_(n) where M is hafnium orzirconium and each L is independently selected from the group consistingof halide (F, Cl, Br, I), alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl,silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino,phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates,nitrates, sulphates, and combinations thereof. n is 4, typically. It iswell known that hafnium metal typically contains some amount of impurityof zirconium. Thus, this invention uses as pure hafnium or zirconium asis commercially reasonable. Specific examples of suitable hafnium andzirconium precursors include, but are not limited to HfCl₄, Hf(CH₂Ph)₄,Hf(CH₂CMe₃)₄, Hf(CH₂SiMe₃)₄, Hf(CH₂Ph)₃Cl, Hf(CH₂CMe₃)₃Cl,Hf(CH₂SiMe₃)₃Cl, Hf(CH₂Ph)₂Cl₂, Hf(CH₂CMe₃)₂)Cl₂, Hf(CH₂SiMe₃)₂Cl₂,Hf(NMe₂)₄, Hf(NEt₂)₄, and Hf(N(SiMe₃)₂)₂Cl₂; ZrCl₄, Zr(CH₂Ph)₄,Zr(CH₂CMe₃)₄, Zr(CH₂SiMe₃)₄, Zr(CH₂Ph)₃Cl, Zr(CH₂CMe₃)₃Cl,Zr(CH₂SiMe₃)₃Cl, Zr(CH₂Ph)₂Cl₂, Zr(CH₂CMe₃)₂Cl₂, Zr(CH₂SiMe₃)₂Cl₂,Zr(NMe₂)₄, Zr(Net₃)₄, Zr(NMe₂)₂Cl₂, Zr(NEt₂)₂Cl₂, and Zr(N(SiMe₃)₂)₂Cl₂.Lewis base adducts of these examples are also suitable as hafniumprecursors, for example, ethers, amines, thioethers, phosphines and thelike are suitable as Lewis bases.

The ligand to metal precursor compound ratio is typically in the rangeof about 0.01:1 to about 100:1, more preferably in the range of about0.1:1 to about 10:1.

Metal-Ligand Complexes

Generally, the ligand is mixed with a suitable metal precursor compoundprior to or simultaneously with allowing the mixture to be contactedwith the reactants (e.g., monomers). When the ligand is mixed with themetal precursor compound, a metal-ligand complex may be formed, whichmay be a catalyst or may need to be activated to be a catalyst. Themetal-ligand complexes discussed herein are referred to as 2,1 complexesor 3,2 complexes, with the first number representing the number ofcoordinating atoms and second number representing the charge occupied onthe metal. The 2,1-complexes therefore have two coordinating atoms and asingle anionic charge. Other embodiments of this invention are thosecomplexes that have a general 3,2 coordination scheme to a metal center,with 3,2 referring to a ligand that occupies three coordination sites onthe metal and two of those sites being anionic and the remaining sitebeing a neutral Lewis base type coordination.

Looking first at the 2,1-nonmetallocene metal-ligand complexes, themetal-ligand complexes may be characterized by the following generalformula:

wherein T, J″, R¹, L and n are as defined previously; and x is 1 or 2.The J″ heteroaryl may or may not datively bond, but is drawn as bonding.More specifically, the nonmetallocene-ligand complexes may becharacterized by the formula:

wherein R¹, T, R⁴, R⁵, R⁶, R⁷, L and n are as defined previously; and xis 1 or 2. In one preferred embodiment x=1 and n=3. Additionally, Lewisbase adducts of these metal-ligand complexes are also within the scopeof the invention, for example, ethers, amines, thioethers, phosphinesand the like are suitable as Lewis bases.

More specifically, the nonmetallocene metal-ligand complexes may becharacterized by the general formula:

wherein the variables are generally defined above. Thus, e.g., Q², Q³,Q⁴, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, nitro, and combinations thereof;optionally, two or more R⁴, R⁵, R⁶, R⁷ groups may be joined to form afused ring system having from 3-50 non-hydrogen atoms in addition to thepyridine ring, e.g. generating a quinoline group; also, optionally, anycombination of R², R³ and R⁴ may be joined together in a ring structure;Q¹ and Q⁵ are selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl,provided that Q¹ and Q⁵ are not both methyl; and each L is independentlyselected from the group consisting of halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkylheterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl,silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino,phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates,nitrates, sulphates and combinations thereof; n is 1, 2, 3, 4, 5, or 6;and x=1 or 2.

In other embodiments, the 2,1 metal-ligand complexes can becharacterized by the general formula:

wherein the variables are generally defined above.

In still other embodiments, the 2,1 metal-ligand complexes can becharacterized by the general formula:

wherein the variables are generally defined above.

The more specific embodiments of the nonmetallocene metal-ligandcomplexes of formulas VI, VII, VIII, IX and X are explained above withregard to the specifics described for the ligands and metal precursors.Specific examples of 2,1 metal-ligand complexes include, but are notlimited to:

where L, n and x are defined as above (e.g., x=1 or 2) and Ph=phenyl. Inpreferred embodiments, x=1 and n=3. Furthermore in preferredembodiments, L is selected from the group consisting of alkyl,substituted alkyl, aryl, substituted aryl or amino.

Turning to the 3,2 metal-ligand nonmetallocene complexes, themetal-ligand complexes may be characterized by the general formula:

where M is zirconium or hafnium;

R¹ and T are defined above;

J′″ being selected from the group of substituted heteroaryls with 2atoms bonded to the metal M, at least one of those 2 atoms being aheteroatom, and with one atom of J′″ is bonded to M via a dative bond,the other through a covalent bond; and

L¹ and L² are independently selected from the group consisting ofhalide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine,hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio,1,3-dionates, oxalates, carbonates, nitrates, sulphates, andcombinations thereof.

More specifically, the 3,2 metal-ligand nonmetallocene complexes may becharacterized by the general formula:

where M is zirconium or hafnium;

T, R¹, R⁴, R⁵, R⁶, L¹ and L² are defined above; and

E″ is either carbon or nitrogen and is part of an cyclic aryl,substituted aryl, heteroaryl, or substituted heteroaryl group.

Even more specifically, the 3,2 metal-ligand nonmetallocene complexesmay be characterized by the general formula:

where M is zirconium or hafnium; and

T, R¹, R⁴, R⁵, R⁶, R¹⁰, R¹¹, R¹², R¹³, L¹ and L² are defined above.

Still even more specifically, the 3,2 metal-ligand nonmetallocenecomplexes may be characterized by the general formula:

where M is zirconium or hafnium; and

T, R¹, R⁴, R⁵, R⁶, R¹⁰, R¹¹, R¹², R¹³, Q¹, Q², Q³, Q⁴, Q⁵, L¹ and L² aredefined above.

The more specific embodiments of the metal-ligand complexes of formulasXI, XII, XIII and XIV are explained above with regard to the specificsdescribed for the ligands and metal precursors.

In the above formulas, R¹⁰, R¹¹, R¹² and R¹³ are independently selectedfrom the group consisting of hydrogen, halo, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinationsthereof; optionally, two or more R¹⁰, R¹¹, R¹² and R¹³ groups may bejoined to form a fused ring system having from 3-50 non-hydrogen atoms.

In addition, Lewis base adducts of the metal-ligand complexes in theabove formulas are also suitable, for example, ethers, amines,thioethers, phosphines and the like are suitable as Lewis bases.

The metal-ligand complexes can be formed by techniques known to those ofskill in the art. In some embodiments, R¹⁴ is hydrogen and themetal-ligand complexes are formed by a metallation reaction (in situ ornot) as shown below in scheme 3:

In scheme 3, R¹⁴ is hydrogen (but see above for the full definition ofR¹⁴ in other embodiments of this invention). The metallation reaction toconvert the 2,1-complex on the left to the 3,2 complex on the right canoccur via a number of mechanisms, likely depending on the substituentschosen for L¹, L² and L³ and the other substituents such as Q¹-Q⁵,R²-R⁶, R¹⁰ to R¹³. In one embodiment, when L¹, L² and L³ are eachN(CH₃)₂, the reaction can proceed by heating the 2,1 complex to atemperature above about 100° C. In this embodiment, it is believed thatL¹ and L² remain N(CH₃)₂ in the 3,2 complex. In another embodiment whereL¹, L² and L³ are each N(CH₃)₂, the reaction can proceed by adding agroup 13 reagent (as described below) to the 2,1 complex at a suitabletemperature (such as room temperature). Preferably the group 13 reagentfor this purpose is di-isobutyl aluminum hydride, tri-isobutyl aluminumor trimethyl aluminum. In this embodiment, L¹ and L² are typicallyconverted to the ligand (e.g., alkyl or hydride) stemming from the group13 reagent (e.g., from trimethyl aluminum, L¹ and L² are each CH₃ in the3,2 complex). The 2,1 complex in scheme 3 is formed by the methodsdiscussed above.

In an alternative embodiment possibly outside the scope of scheme 3, forisotactic polypropylene production, it is currently preferred that R¹⁴is either hydrogen or methyl.

Specific examples of 3,2 complexes include:

The ligands, complexes or catalysts may be supported on an organic orinorganic support. Suitable supports include silicas, aluminas, clays,zeolites, magnesium chloride, polyethyleneglycols, polystyrenes,polyesters, polyamides, peptides and the like. Polymeric supports may becross-linked or not. Similarly, the ligands, complexes or catalysts maybe supported on similar supports known to those of skill in the art. Inaddition, the catalysts described above may be combined with othercatalysts in a single reactor and/or employed in a series of reactors(parallel or serial) in order to form blends of polymer products.Supported catalysts typically produce P/E* copolymers with an MWD largerthan those produce from unsupported catalysts., although these MWDs aretypically less about 6, preferably less than about 5 and more preferablyless than about 4.

The metal complexes are rendered catalytically active by combinationwith an activating cocatalyst or by use of an activating technique.Suitable activating cocatalysts for use herein include neutral Lewisacids such as alumoxane (modified and unmodified), C₁₋₃₀ hydrocarbylsubstituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- ortri(hydrocarbyl)boron compounds and halogenated (includingperhalogenated) derivatives thereof, having from 1 to 10 carbons in eachhydrocarbyl or halogenated hydrocarbyl group, more especiallyperfluorinated tri(aryl)boron compounds, and most especiallytris(pentafluorophenyl)borane; nonpolymeric, compatible,noncoordinating, ion forming compounds (including the use of suchcompounds under oxidizing conditions), especially the use of ammonium-,phosphonium-, oxonium-, carbonium-, silylium- or sulfonium-salts ofcompatible, noncoordinating anions, or ferrocenium salts of compatible,noncoordinating anions; bulk electrolysis (explained in more detailhereinafter); and combinations of the foregoing activating cocatalystsand techniques. The foregoing activating cocatalysts and activatingtechniques have been previously taught with respect to different metalcomplexes in the following references: U.S. Pat. Nos. 5,153,157,5,064,802, 5,721,185 and 5,350,723, and EP-A-277,003 and -A-468,651(equivalent to U.S. Pat. No. 5,321,106).

The alumoxane used as an activating cocatalyst is of the formula (R⁴_(x)(CH₃)_(y)AlO)_(n), in which R⁴ is a linear, branched or cyclic C₁ toC₆ hydrocarbyl, x is from 0 to about 1, y is from about 1 to 0, and n isan integer from about 3 to about 25, inclusive. The preferred alumoxanecomponents, referred to as modified methylaluminoxanes, are thosewherein R⁴ is a linear, branched or cyclic C₃ to C₉ hydrocarbyl, x isfrom about 0.15 to about 0.50, y is from about 0.85 to about 0.5 and nis an integer between 4 and 20, inclusive; still more preferably, R⁴ isisobutyl, tertiary butyl or n-octyl, x is from about 0.2 to about 0.4, yis from about 0.8 to about 0.6 and n is an integer between 4 and 15,inclusive. Mixtures of the above alumoxanes may also be employed.

Most preferably, the alumoxane is of the formula (R⁴_(x)(CH₃)_(y)AlO)_(n), wherein R⁴ is isobutyl or tertiary butyl, x isabout 0.25, y is about 0.75 and n is from about 6 to about 8.

Particularly preferred alumoxanes are so-called modified alumoxanes,preferably modified methylalumoxanes (MMAO), that are completely solublein alkane solvents, for example heptane, and may include very little, ifany, trialkylaluminum. A technique for preparing such modifiedalumoxanes is disclosed in U.S. Pat. No. 5,041,584. Alumoxanes useful asan activating cocatalyst may also be made as disclosed in U.S. Pat. Nos.4,542,199, 4,544,762, 4,960,878, 5,015,749, 5,041,583 and 5,041,585.Various alumoxanes can be obtained from commercial sources, for example,Akzo-Nobel Corporation, and include MMAO-3A, MMAO-12, and PMAO-IP.

Combinations of neutral Lewis acids, especially the combination of atrialkyl aluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to10 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, and combinations of neutral Lewis acids,especially tris(pentafluorophenyl)borane, with nonpolymeric, compatiblenoncoordinating ion-forming compounds are also useful activatingcocatalysts.

Suitable ion forming compounds useful as cocatalysts include a cationwhich is a Bronsted acid capable of donating a proton, and a compatible,noncoordinating anion, A⁻. As used herein, the term “noncoordinating”means an anion or substance which either does not coordinate to theGroup 4 metal containing precursor complex and the catalytic derivativederived therefrom, or which is only weakly coordinated to such complexesthereby remaining sufficiently labile to be displaced by a neutral Lewisbase. A noncoordinating anion specifically refers to an anion which whenfunctioning as a charge balancing anion in a cationic metal complex doesnot transfer an anionic substituent or fragment thereof to said cationthereby forming neutral complexes. “Compatible anions” are anions whichare not degraded to neutrality when the initially formed complexdecomposes and are noninterfering with desired subsequent polymerizationor other uses of the complex.

Preferred anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitrites. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions which comprise coordination complexescontaining a single metal or metalloid atom are, of course, well knownand many, particularly such compounds containing a single boron atom inthe anion portion, are available commercially.

In one embodiment, the activating cocatalysts may be represented by thefollowing general formula:[L*−H]⁺ _(d)[A^(d−)]wherein:

-   -   L* is a neutral Lewis base;    -   [L*-H]⁺ is a Bronsted acid;    -   A^(d−) is a noncoordinating, compatible anion having a charge of        d⁻, and    -   d is an integer from 1 to 3.        More preferably A^(d−) corresponds to the formula:        [M′^(k+)Q_(n)′]^(d−) wherein:    -   k is an integer from 1 to 3;    -   n′ is an integer from 2 to 6;    -   n′−k=d;    -   M′ is an element selected from Group 13 of the Periodic Table of        the Elements; and    -   Q independently each occurrence is selected from hydride,        dialkylamido, halide, hydrocarbyl, hydrocarbyloxy,        halosubstituted-hydrocarbyl, halosubstituted hydrocarbyloxy, and        halo substituted silylhydrocarbyl radicals (including        perhalogenated hydrocarbyl-perhalogenated hydrocarbyloxy- and        perhalogenated silylhydrocarbyl radicals), said Q having up to        20 carbons with the proviso that in not more than one occurrence        is Q halide. Examples of suitable hydrocarbyloxide Q groups are        disclosed in U.S. Pat. No. 5,296,433.

In a more preferred embodiment, d is one, i. e., the counter ion has asingle negative charge and is A⁻. Activating cocatalysts comprisingboron which are particularly useful in the preparation of thesecatalysts may be represented by the following general formula:[L*−H]⁺[BQ₄]⁻wherein:

-   -   [L*−H]⁺is as previously defined;    -   B is boron in an oxidation state of 3; and    -   Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-,        fluorinated hydrocarbyloxy- or fluorinated        silylhydrocarbyl-group of up to 20 nonhydrogen atoms, with the        proviso that in not more than one occasion is Q hydrocarbyl.        Most preferably, Q is each occurrence a fluorinated aryl group,        especially, a pentafluorophenyl group.

Illustrative, but not limiting, examples of boron compounds which may beused as an activating cocatalyst in the preparation of the catalysts aretri-substituted ammonium salts such as:

-   triethylammonium tetraphenylborate,-   N,N-dimethylanilinium tetraphenylborate,-   tripropylammonium tetrakis(pentafluorophenyl)borate,-   N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate,-   triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,-   N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, and-   N,N-dimethyl-2,4,6-trimethylanilinium    tetrakis(2,3,4,6-tetrafluorophenyl)borate;    dialkyl ammonium salts such as:-   di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, and-   dicyclohexylammonium tetrakis(pentafluorophenyl)borate;    tri-substituted phosphonium salts such as:-   triphenylphosphonium tetrakis(pentafluorophenyl)borate,-   tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, and-   tri(2,6-dimethylphenyl)phosphonium    tetrakis(pentafluorophenyl)borate;    di-substituted oxonium salts such as:-   diphenyloxonium tetrakis(pentafluorophenyl)borate,-   di(o-tolyl)oxonium tetrakis(pentafluorophenyl)borate, and-   di(2,6-dimethylphenyl)oxonium tetrakis(pentafluorophenyl)borate;    di-substituted sulfonium salts such as:-   diphenylsulfonium tetrakis(pentafluorophenyl)borate,-   di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, and-   di(2,6-dimethylphenyl)sulfonium tetrakis(pentafluorophenyl)borate.

Preferred [L*-H]⁺ cations are N,N-dimethylanilinium andtributylammonium.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:(Ox^(e+))_(d)(A^(d−))_(e)wherein:

-   -   Ox^(e+) is a cationic oxidizing agent having a charge of e⁺;    -   e is an integer from 1 to 3; and    -   A^(d−) and d are as previously defined.        Examples of cationic oxidizing agents include: ferrocenium,        hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Preferred        embodiments of A^(d−) are those anions previously defined with        respect to the Bronsted acid containing activating cocatalysts,        especially tetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst comprises a compoundwhich is a salt of a carbenium ion and a noncoordinating, compatibleanion represented by the formula:©⁺A⁻wherein:

-   -   ©⁺ is a C₁₋₂₀ carbenium ion; and    -   A⁻ is as previously defined.        A preferred carbenium ion is the trityl cation, i.e.,        triphenylmethylium.

A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:R₃Si(X′)_(q) ⁺A⁻wherein:

R is C₁₋₁₀ hydrocarbyl, and X′, q and A⁻ are as previously defined.

Preferred silylium salt activating cocatalysts are trimethylsilyliumtetrakis(pentafluorophenyl)borate,triethylsilylium(tetrakispentafluoro)phenylborate and ether substitutedadducts thereof. Silylium salts have been previously genericallydisclosed in J. Chem Soc. Chem. Comm., 1993, 383-384, as well asLambert, J. B., et al., Organometallics, 1994, 13, 2430-2443.

Certain complexes of alcohols, mercaptans, silanols, and oximes withtris(pentafluorophenyl)borane are also effective catalyst activators.Such cocatalysts are disclosed in U.S. Pat. No. 5,296,433.

The metal complexes can also be rendered catalytically active by bulkelectrolysis or the generation of activating cocatalysts by theelectrolysis of a disilane compound in the presence of a source of anoncoordinating compatible anion. This latter technique is more fullydisclosed in U.S. Pat. No. 5,625,087.

The foregoing activating techniques and ion forming cocatalysts are alsopreferably used in combination with a tri(hydrocarbyl)aluminum ortri(hydrocarbyl)borane compound having from 1 to 4 carbons in eachhydrocarbyl group.

The molar ratio of catalyst/cocatalyst employed preferably ranges from1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferablyfrom 1:100 to 1:1. In one embodiment, the cocatalyst can be used incombination with a tri(hydrocarbyl)aluminum compound having from 1 to 10carbons in each hydrocarbyl group. Mixtures of activating cocatalystsmay also be employed. These aluminum compounds can be employed for theirbeneficial ability to scavenge impurities such as oxygen, water, andaldehydes from the polymerization mixture. Preferred aluminum compoundsinclude trialkyl aluminum compounds having from 1 to 6 carbons in eachalkyl group, especially those wherein the alkyl groups are methyl,ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl orisopentyl. The molar ratio of metal complex to aluminum compound ispreferably from 1:10,000 to 100:1, more preferably from 1:1000 to 10:1,most preferably from 1:500 to 1:1. A most preferred borane activatingcocatalyst comprises a strong Lewis acid, especiallytris(pentafluorophenyl)borane.

The catalyst system may be prepared as a homogeneous catalyst byaddition of the requisite components to a solvent in whichpolymerization will be carried out by solution polymerizationprocedures. The catalyst system may also be prepared and employed as aheterogeneous catalyst by adsorbing the requisite components on acatalyst support material such as silica gel, alumina or other suitableinorganic support material. When prepared in heterogeneous or supportedform, it is preferred to use silica as the support material. Theheterogeneous form of the catalyst system may be employed in a slurry orgas phase polymerization.

In some embodiments, the nonmetallocene catalysts described herein maybe utilized in combination with at least one additional homogeneous orheterogeneous polymerization catalyst in separate reactors connected inseries or in parallel to prepare polymer blends having desirableproperties. An example of such a process is disclosed in WO 94/00500,equivalent to U.S. Ser. No. 07/904,770, as well as U.S. Ser. No.08/10958. Included in these embodiments is the use of two differentnonmetallocene, metal-centered, heteroaryl ligand catalysts. Anycatalyst which is capable of copolymerizing one or more olefin monomersto make an interpolymer or homopolymer may be used in conjunction withthe nonmetallocene, metal-centered, heteroaryl ligand catalyst. Onesuitable class of catalysts is the metallocene catalysts disclosed inU.S. Pat. Nos. 5,044,438, 5,057,475, 5,096,867 and 5,324,800.

Another suitable class of catalysts is substituted indenyl containingmetal complexes as disclosed in U.S. Pat. Nos. 5,965,756 and 6,015,868.Other catalysts are disclosed in U.S. Pat. Nos. 6,268,444 and 6,515,155and in U.S. Patent Application Publication Numbers 2002/0062011,2003/0004286 and 2002/0165329, and in copending application U.S. Ser.No. 60/393,862. These catalysts tend to have the capability of producinghigher molecular weight polymers.

Other catalysts, cocatalysts, catalyst systems, and activatingtechniques which may be used to make the impact-modifying polymers usedin the practice of the invention include those disclosed in WO 96/23010,99/14250, 98/41529 and 97/42241; Scollard, et al., in J. Am. Chem. Soc1996, 118, 10008-10009; EP 0 468 537 B1; WO 97/22635; EP 0 949 278 A2, 0949 279 A2, and 1 063 244 A2; U.S. Pat. Nos. 5,408,017, 5,767,208 and5,907,021; WO 88/05792, 88/05793 and 93/25590; U.S. Pat. Nos. 5,599,761and 5,218,071; WO 90/07526; U.S. Pat. Nos. 5,972,822, 6,074,977,6,013,819, 5,296,433, 4,874,880, 5,198,401, 5,621,127, 5,703,257,5,728,855, 5,731,253, 5,710,224, 5,883,204, 5,504,049, 5,962,714,5,965,677 and 5,427,991; WO 93/21238, 94/03506, 93/21242, 94/00500,96/00244 and 98/50392; Wang, et al., Organometallics 1998, 17,3149-3151; Younkin, et al., Science 2000, 287, 460-462; Chen and Marks,Chem. Rev. 2000, 100, 1391-1434; Alt and Koppl, Chem. Rev. 2000, 100,1205-1221; Resconi, et al., Chem. Rev. 2000, 100, 1253-1345; Ittel, etal., Chem Rev. 2000, 100, 1169-1203; Coates, Chem. Rev., 2000, 100,1223-1251; U.S. Pat. Nos. 5,093,415, 6,303,719 and 5,874,505; and WO96/13530. Also useful are those catalysts, cocatalysts and catalystsystems disclosed in U.S. Pat. Nos. 6,268,444, 6,515,155, U.S. Pat. Nos.5,965,756 and 6,150,297. CGC and other catalysts that make amphorouspolymers are not favored for use in this invention.

Process Descriptions

The matrix polymers, including the P* homopolymer, and the impactmodifying polymers, including the P/E* copolymers, used in the practiceof this invention can be made by any convenient process. In oneembodiment, the process reagents, e.g., (i) propylene, (ii) ethyleneand/or one or more unsaturated comonomers, (iii) catalyst, and, (iv)optionally, solvent and/or a molecular weight regulator (e.g.,hydrogen), are fed to a single reaction vessel of any suitable design,e.g., stirred tank, loop, fluidized-bed, etc. The process reagents arecontacted within the reaction vessel under appropriate conditions (e.g.,solution, slurry, gas phase, suspension, high pressure) to form thedesired polymer, and then the output of the reactor is recovered forpost-reaction processing. All of the output from the reactor can berecovered at one time (as in the case of a single pass or batchreactor), or it can be recovered in the form of a bleed stream whichforms only a part, typically a minor part, of the reaction mass (as inthe case of a continuous process reactor in which an output stream isbled from the reactor at the same rate at which reagents are added tomaintain the polymerization at steady-state conditions). “Reaction mass”means the contents within a reactor, typically during or subsequent topolymerization. The reaction mass includes reactants, solvent (if any),catalyst, and products and by-products. The recovered solvent andunreacted monomers can be recycled back to the reaction vessel.

The polymerization conditions at which the reactor is operated aresimilar to those for the polymerization of propylene using a known,conventional Ziegler-Natta catalyst. Typically, solution polymerizationof propylene is performed at a polymerization temperature between about−50 to about 200, preferably between about −10 and about 150, C, andmore preferably between about 20 to about 150 C and most preferablybetween about 80 and 150 C, and the polymerization pressure is typicallybetween about atmospheric to about 7, preferably between about 0.2 andabout 5, Mpa. If hydrogen is present, then it is usually present at apartial pressure (as measured in the gas phase portion of thepolymerization) of about 0.1 kPa to about 5 Mpa, preferably betweenabout 1 kPa to about 3 Mpa. Gas phase, suspension and otherpolymerization schemes will use conditions conventional for thoseschemes. For gas-phase or slurry-phase polymerization processes, it isdesirable to perform the polymerization at a temperature below themelting point of the polymer.

For the propylene/ethylene copolymer processes described herein,optionally containing additional unsaturated monomer, the weight ratioof propylene to ethylene in the feed to the reactors is preferably inthe range of 10,000:1 to 1;10, more preferably 1,000:1 to 1:1, stillmore preferably 500:1 to 3:1. For the propylene/C₄₋₂₀ α-olefin copolymerprocesses of the present invention, the weight ratio of propylene toC₄₋₂₀ α-olefin in the feed preferably is in the range of 10,000:1 to1:20, more preferably 1,000:1 to 1:1, still more preferably 1,000:1 to3:1.

The post-reactor processing of the recover reaction mass from thepolymerization vessel typically includes the deactivation of thecatalyst, removal of catalyst residue, drying of the product, and thelike. The recovered polymer is then ready for storage and/or use.

The P* and P/E* polymers produced in a single reaction vessel will havethe desired MFR, narrow MWD and, if a P/E* polymer, the ¹³C NMR peaks at14.6 and 15.7 ppm (the peaks of approximately equal intensity), a highB-value (if a P/E* copolymer), and/or other defining characteristics.If, however, a broader MWD is desired, e.g., a MWD of between about 2.5and about 3.5 or even higher, without any substantial change to theother defining characteristics of the propylene copolymer, then thecopolymer is preferably made in a multiple reactor system. In multiplereactor systems, MWD as broad as 15, more preferably 10, most preferably4-8, can be prepared.

In one embodiment, the monomers comprise propylene and at least oneolefin selected from the group consisting of C₄-C₁₀ α-olefins,especially 1-butene, 1-hexene, and 1-octene, and the melt flow rate(MFR) of the interpolymer is preferably in the range of about 0.1 toabout 500, more preferably in the range from about 0.1 to about 100,further more preferably about 0.2 to 80, most preferably in the range of0.3-50.

As a practical limitation, slurry polymerization takes place in liquiddiluents in which the polymer product is substantially insoluble.Preferably, the diluent for slurry polymerization is one or morehydrocarbons with less than 5 carbon atoms. If desired, saturatedhydrocarbons such as ethane, propane or butane may be used in whole orpart as the diluent. Likewise the α-olefin comonomer or a mixture ofdifferent α-olefin comonomers may be used in whole or part as thediluent. Most preferably, the major part of the diluent comprises atleast the α-olefin monomer or monomers to be polymerized.

Solution polymerization conditions utilize a solvent for the respectivecomponents of the reaction. Preferred solvents include, but are notlimited to, mineral oils and the various hydrocarbons which are liquidat reaction temperatures and pressures. Illustrative examples of usefulsolvents include, but are not limited to, alkanes such as pentane,iso-pentane, hexane, heptane, octane and nonane, as well as mixtures ofalkanes including kerosene and Isopar E™, available from Exxon ChemicalsInc.; cycloalkanes such as cyclopentane, cyclohexane, andmethylcyclohexane; and aromatics such as benzene, toluene, xylenes,ethylbenzene and diethylbenzene.

The polymerization may be carried out as a batch or a continuouspolymerization process. A continuous process is preferred, in whichevent catalysts, solvent or diluent (if employed), and comonomers (ormonomer) are continuously supplied to the reaction zone and polymerproduct continuously removed therefrom. The polymerization conditionsfor manufacturing the impact modifying polymers used in the practice ofthis invention are generally those useful in the solution polymerizationprocess, although the application is not limited thereto. Gas phase andslurry polymerization processes are also believed to be useful, providedthe proper catalysts and polymerization conditions are employed.

The following procedure may be carried out to obtain a P/E* copolymer:In a stirred-tank reactor propylene monomer is introduced continuouslytogether with solvent, and ethylene monomer. The reactor contains aliquid phase composed substantially of ethylene and propylene monomerstogether with any solvent or additional diluent. If desired, a smallamount of a “H”-branch inducing diene such as norbornadiene,1,7-octadiene or 1,9-decadiene may also be added. A nonmetallocene,metal-centered, heteroaryl ligand catalyst and suitable cocatalyst arecontinuously introduced in the reactor liquid phase. The reactortemperature and pressure may be controlled by adjusting thesolvent/monomer ratio, the catalyst addition rate, as well as by coolingor heating coils, jackets or both. The polymerization rate is controlledby the rate of catalyst addition. The ethylene content of the polymerproduct is determined by the ratio of ethylene to propylene in thereactor, which is controlled by manipulating the respective feed ratesof these components to the reactor. The polymer product molecular weightis controlled, optionally, by controlling other polymerization variablessuch as the temperature, monomer concentration, or by a stream ofhydrogen introduced to the reactor, as is known in the art. The reactoreffluent is contacted with a catalyst kill agent, such as water. Thepolymer solution is optionally heated, and the polymer product isrecovered by flashing off unreacted gaseous ethylene and propylene aswell as residual solvent or diluent at reduced pressure, and, ifnecessary, conducting further devolatilization in equipment such as adevolatilizing extruder or other devolatilizing equipment operated atreduced pressure. For a solution polymerization process, especially acontinuous solution polymerization, preferred ranges of propyleneconcentration at steady state are from about 0.05 weight percent of thetotal reactor contents to about 50 weight percent of the total reactorcontents, more preferably from about 0.5 weight percent of the totalreactor contents to about 30 weight percent of the total reactorcontents, and most preferably from about 1 weight percent of the totalreactor contents to about 25 weight percent of the total reactorcontents. The preferred range of polymer concentration (otherwise knownas % solids) is from about 3% of the reactor contents by weight to about45% of the reactor contents or higher, more preferably from about 10% ofthe reactor contents to about 40% of the reactor contents, and mostpreferably from about 15% of the reactor contents to about 40% of thereactor contents.

In a continuous process, the mean residence time of the catalyst andpolymer in the reactor generally is from 5 minutes to 8 hours, andpreferably from 10 minutes to 6 hours, more preferably from 10 minutesto 1 hour.

In some embodiments, ethylene is added to the reaction vessel in anamount to maintain a differential pressure in excess of the combinedvapor pressure of the propylene and diene monomers. The ethylene contentof the polymer is determined by the ratio of ethylene differentialpressure to the total reactor pressure. Generally the polymerizationprocess is carried out with a pressure of ethylene of from 10 to 1000psi (70 to 7000 kPa), most preferably from 40 to 800 psi (30 to 600kPa). The polymerization is generally conducted at a temperature of from25 to 250° C., preferably from 75 to 200° C., and most preferably fromgreater than 95 to 200° C.

In another embodiment, a process for producing a propylene homopolymeror interpolymer of propylene with at least one additional olefinicmonomer selected from ethylene or C₄₋₂₀ α-olefins comprises thefollowing steps: 1) providing controlled addition of a nonmetallocene,metal-centered, heteroaryl ligand catalyst to a reactor, including acocatalyst and optionally a scavenger component; 2) continuously feedingpropylene and optionally one or more additional olefinic monomersindependently selected from ethylene or C₄₋₂₀ α-olefins into thereactor, optionally with a solvent or diluent, and optionally with acontrolled amount of H₂; and 3) recovering the polymer product.Preferably, the process is a continuous solution process. Thecocatalysts and optional scavenger components in the novel process canbe independently mixed with the catalyst component before introductioninto the reactor, or they may each independently be fed into the reactorusing separate streams, resulting in “in reactor” activation. Scavengercomponents are known in the art and include, but are not limited to,alkyl aluminum compounds, including alumoxanes. Examples of scavengersinclude, but are not limited to, trimethyl aluminum, triethyl aluminum,triisobutyl aluminum, trioctyl aluminum, methylalumoxane (MAO), andother alumoxanes including, but not limited to, MMAO-3A, MMAO-7, PMAO-IP(all available from Akzo Nobel).

By proper selection of process conditions, including catalyst selection,polymers with tailored properties can be produced. For a solutionpolymerization process, especially a continuous solution polymerization,preferred ranges of ethylene concentration at steady state are from lessthan about 0.02 weight percent of the total reactor contents to about 5weight percent of the total reactor contents, and the preferred range ofpolymer concentration is from about 10% of the reactor contents byweight to about 45% of the reactor contents or higher.

In general, catalyst efficiency (expressed in terms of gram of polymerproduced per gram of transition metal) decreases with increasingtemperature and decreasing ethylene concentration. In addition, themolecular weight of the polymer product generally decreases withincreasing reactor temperature and decreases with decreasing propyleneand ethylene concentration. The molecular weight of the polyolefin canalso be controlled with the addition of chain transfer compounds,especially through the addition of H₂.

Applications

The impact-modified blends of this invention possess a balance ofstiffness, toughness and optics that is desirable for many end uses.They are particularly preferred for applications where excellent clarityis required in combination with the improved toughness via impactmodification. Examples of such applications include extrusion to makecast sheet, cast film and blown film; solid-phase pressure forming andmelt thermoforming of cast sheet; and molding processes such asinjection molding, rotomolding, and especially extrusion blow moldingand injection stretch blow molding. Moreover, certain impact modifyingP/E* terpolymers exhibit lower haze values than their comparable P/E*copolymer counterparts when blended with a crystalline polypropylene insimilar amounts and under similar conditions.

The impact modifying polymers used in the practice of this invention canalso be functionalized by adding one or more functional groups, e.g.through the use of a functionalized azide, to the polymer chain in apost-reaction operation. Optionally, the impact modifiers used in thepractice of this invention can be subjected to post-reaction treatments,e.g. crosslinking, vis-breaking, and the like. Vis-breaking isparticularly useful in reducing the viscosity of high molecular weightpolymers. These post treatments are also used in their conventionalmanner.

The following examples are given to illustrate various embodiments ofthe invention. They do not intend to limit the invention as otherwisedescribed and claimed herein. All numerical values are approximate. Whena numerical range is given, it should be understood that embodimentsoutside the range are still within the scope of the invention unlessotherwise indicated. In the following examples, various polymers werecharacterized by a number of methods. Performance data of these polymerswere also obtained. Most of the methods or tests were performed inaccordance with an ASTM standard, if applicable, or known procedures.All parts and percentages are by weight unless otherwise indicated FIGS.10A-B illustrate the chemical structures of various catalysts describedin the following examples.

SPECIFIC EMBODIMENTS

Tetrahydrofuran (THF), diethyl ether, toluene, hexane, and ISOPAR E(obtainable from Exxon Chemicals) are used following purging with pure,dry nitrogen and passage through double columns charged with activatedalumina and alumina supported mixed metal oxide catalyst (Q-5 catalyst,available from Engelhard Corp). All syntheses and handling of catalystcomponents are performed using rigorously dried and deoxygenatedsolvents under inert atmospheres of nitrogen or argon, using eitherglove box, high vacuum, or Schlenk techniques, unless otherwise noted.MMAO-3A, PMAO, and PMAO-IP can be purchased from Akzo-Nobel Corporation.

Synthesis of (C₅Me₄SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) (Catalyst A, FIG.10A)

Catalyst A can be synthesized according to Example 17 of U.S. Pat. No.5,556,928.

Synthesis of dimethylsilyl(2-methyl-s-indacenyl)(t-butylamido)titanium1,3-pentadiene (Catalyst B, FIG. 10B)

Catalyst B can be synthesized according to Example 23 of U.S. Pat. No.5,965,756.

Synthesis of(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium(Catalyst C, FIG. 10C)

(1) Preparation ofdichloro(N-(1,1-dimethylethyl)-1,1-di(p-tolyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium

(A) Preparation ofN-(tert-butyl)-N-(1,1-p-tolyl)-1-(3-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amine:

To a 1.70 g (5.35 mmol) ofN-(tert-butyl)-N-(1-chloro-1,1-di(3-p-tolyl)silylamine dissolved in 20mL of THF is added 1.279 g (5.35 mmol) of1-(1H-3-indenyl)-1-(2,3-dihydro-1H-isoindolinyl) lithium salt dissolvedin 20 mL of THF. After the addition, the reaction mixture is stirred for9 hours and then solvent is removed under reduced pressure. The residueis extracted with 40 mL of hexane and filtered. Solvent is removed underreduced pressure giving 2.806 of product as a gray solid.

¹H (C₆D₆) δ: 1.10 (s, 9H), 2.01 (s, 3H), 2.08 (s, 3H), 4.12 (d, 1H,³J_(H-H)=1.5 Hz), 4.39 (d, 1H, ²J_(H-H)=11.1 Hz), 4.57 (d, 1H,²J_(H-H)=11.7 Hz), 5.55 (d, 1H, ³J_(H-H)=2.1 Hz), 6.9-7.22 (m, 10H),7.56 (d, 1H, ³J_(H-H)=7.8 Hz), 7.62 (d, 1H, ³J_(H-H)=6.9 Hz), 7.67 (d,1H, ³J_(H-H)=7.8 Hz), 7.83 (d, 1H, ³J_(H-H)=7.8 Hz).

¹³C{¹H} (C₆D₆) δ: 21.37, 21.43, 33.78, 41.09, 50.05, 56.56, 104.28,120.98, 122.46, 123.84, 124.71, 124.84, 126.98, 128.29, 128.52, 129.05,132.99, 133.68, 135.08, 135.90, 136.01, 138.89, 139.05, 139.09, 141.27,146.39, 148.48.

(B) Preparation ofN-(tert-butyl)-N-(1,1-p-tolyl)-1-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amine,dilithium salt:

To a 50 mL hexane solution containing 2.726 g (5.61 mmol) of theN-(tert-butyl)-N-(1,1-p-tolyl)-1-(3-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amineis added 7.4 mL of 1.6 M n-BuLi solution. During addition of the n-BuLi,a yellow precipitate appears. After stirring for 6 hours, the yellowprecipitate is collected on a frit, washed with 2×25 mL of hexane, anddried under reduced pressure to give 2.262 g of the product as a yellowpowder.

¹H (C₆D₆) δ: 1.17 (s, 9H), 2.30 (s, 6H), 4.51 (s, 4H), 6.21 (s, 1H),6.47 (m, 2H), 6.97 (d, 4H, ³J_(H-H)=8.1 Hz), 7.15 (m, 2H), 7.23 (m, 2H),7.50 (m, 1H), 7.81 (d, 4H, ³J_(H-H)=7.8 Hz), 8.07 (d, 1H, ³J_(H-H)=7.2Hz). ¹³C{¹H} (C₆D₆) δ: 21.65, 38.83, 52.46, 59.82, 95.33, 112.93,114.15, 115.78, 118.29, 122.05, 122.60, 124.16, 124.78, 126.94, 127.30,133.06, 134.75, 137.30, 141.98, 148.17.

(C) Preparation ofdichloro(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium:

In the drybox 1.552 g (4.19 mmol) of TiCl₃(THF) 3 is suspended in 20 mLof THF. To this solution, 2.206 g (4.19 mmol) ofN-(tert-butyl)-N-(1,1-p-tolyl)-1-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amine,dilithium salt dissolved in 30 mL of THF is added within 1 minute. Thesolution is then stirred for 60 minutes. After this time, 0.76 g ofPbCl₂ (2.75 mmol) is added and the solution is stirred for 60 minutes.The THF is then removed under reduced pressure. The residue is firstextracted with 60 mL of methylene chloride and filtered. Solvent isremoved under reduced pressure leaving a black crystalline solid. Hexaneis added (30 mL) and the black suspension is stirred for 10 hour. Thesolids are collected on a frit, washed with 30 mL of hexane and driedunder reduced pressure to give 2.23 g of the desired product as a deeppurple solid.

¹H (THF-d₈) δ: 1.40 (s, 9H), 2.46 (s, 3H), 2.48 (s, 3H), 5.07 (d, 2H,²J_(H-H)=12.3 Hz), 5.45 (d, 2H, ²J_(H-H)=12.6 Hz), 5.93 (s, 1H), 6.95(d, 1H, ³J_(H-H)=9.0 Hz), 7.08 (d, 1H), ³J_(H-H)=7.8 Hz), 7.15-7.4 (m,9H), 7.76 (d, 1H, ³J_(H-H)=7.8 Hz), 7.82 (d, 1H, ³J_(H-H)=7.5 Hz), 8.05(d, 1H, ³J_(H-H)=8.7 Hz). ¹³C{¹H} (THF-d₈) δ: 21.71, 21.76, 33.38,56.87, 61.41, 94.5, 107.95, 122.86, 125.77, 126.68, 127.84, 127.92,128.40, 128.49, 129.36, 129.79, 131.23, 131.29, 135.79, 136.43, 136.73,141.02, 141.22, 150.14.

(2) Preparation of(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium:

In the drybox 0.50 g ofdichloro(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titaniumcomplex (0.79 mmol) is dissolved in 30 mL of diethyl ether. To thissolution, 1.14 mL (1.6 mmol) of MeLi (1.6 M in ether) is added dropwisewhile stirring over a 1 minute period. After the addition of MeLi iscompleted, the solution is stirred for 1.5 hour. Diethyl ether isremoved under reduced pressure and the residue extracted with 45 mL ofhexane. Hexane is removed under reduced pressure giving a redcrystalline material. This solid is dissolved in about 7 mL of tolueneand 25 mL of hexane, filtered, and the solution was put into the freezer(−27° C.) for 2 days. The solvent is then decanted and the resultingcrystals are washed with cold hexane and dried under reduced pressure togive 156 mg of product.

¹H (C₆D₆) δ: 0.25 (s, 3H), 0.99 (3H), 1.72 (s, 9H), 2.12 (s, 3H), 2.15(s, 3H), 4.53 (d, 2H, ²J_(H-H)=11.7 Hz), 4.83 (d, 2H, ²J_(H-H)=11.7 Hz),5.68 (s, 1H), 6.72 (dd, 1H, ³J_(H-H)=8.6 Hz, ³J_(H-H)=6.6 Hz), 6.9-7.2(m, 11H), 7.30 (d, 1H, ³J_(H-H)=8.6 Hz). 7.71 (d, 1H, ³J_(H-H)=8.5 Hz),7.93 (d, 1H, ³J_(H-H)=7.8 Hz), 8.11 (d, 1H, ³J_(H-H)=7.8 Hz). ¹³C{¹H}(C₆D₆) δ: 21.45, 21.52, 35.30, 50.83, 56.03, 56.66, 57.65, 83.80,105.64, 122.69, 124.51, 124.56, 125.06, 125.35, 127.33, 128.98, 129.06,129.22, 133.51, 134.02, 134.62, 136.49, 136.84, 137.69, 139.72, 139.87,143.84.

Synthesis of(1H-cyclopenta[1]phenanthrene-2-yl)dimethyl(t-butylamido)silane titaniumdimethyl (Catalyst D, FIG. 10D)

Catalyst D can be synthesized according to Example 2 of U.S. Pat. No.6,150,297.

Synthesis ofrac-[dimethylsilylbis(1-(2-methyl-4-phenyl)indenyl)]zirconium(1,4-diphenyl-1,3-butadiene) (Catalyst E, FIG. 10E)

Catalyst E can be synthesized according to Example 15 of U.S. Pat. No.5,616,664.

Synthesis ofrac-[1,2-ethanediylbis(1-indenyl)]zirconium(1,4-diphenyl-1,3-butadiene)(Catalyst F, FIG. 10F)

Catalyst F can be synthesized according to Example 11 of U.S. Pat. No.5,616,664.

Synthesis of Catalyst G, FIG. 10G

Hafnium tetrakisdimethylamine. The reaction is prepared inside of a drybox. A 500 mL round bottom flask containing a stir bar, is charged with200 mL of toluene and LiNMe₂ (21 g, 95%, 0.39 mol). HfCl₄ (29.9 g, 0.093mol) is added slowly over 2 h. The temperature reaches 55° C. Themixture is stirred overnight at ambient temperature. The LiCl isfiltered off. The toluene is carefully distilled away from the product.Final purification is achieved by distillation with a vacuum transferline attached to a cold (−78° C.) receiving flask. This process isperformed outside the dry box on a Schlenk line. The material isdistilled over at 110-120° C. at 300-600 microns. The 19.2 g of thewhite solid is collected.

2-formyl-6-naphthylpyridine. Inside of a dry box, naphthylboronic acid(9.12 g, 53.0 mmol) and Na₂CO₃ (11.64 g, 110 mmol) are dissolved in 290mL of degassed 4:1 H₂O/MeOH. This solution is added to a solution of 8 g(43 mmol) of 2-bromo-6-formylpyridine and 810 mg (0.7 mmol) of Pd(PPh₃)₄in 290 mL of degassed toluene. The charged reactor is removed from thedry box, while under a blanket of N₂ and is connected to the house N₂line. The biphasic solution is vigorously stirred and heated to 70° C.for 4 h. On cooling to RT, the organic phase is separated. The aqueouslayer is washed with 3×75 mL of Et₂O. The combined organic extracts arewashed with 3×100 mL of H₂O and 1×100 mL of brine and dried over Na₂SO₄.After removing the volatiles in vacuo, the resultant light yellow oil ispurified via trituration with hexanes. The isolated material isrecrystallized from a hot hexane solution and ultimately yielded 8.75 g,87% yield. mp 65-66° C.

¹H NMR (CDCl₃) δ 7.2-8.3 (m, 10H), 10.25 (s, 1 H) ppm. ¹³C NMR (CDCl₃)120.3, 125.64, 125.8, 126.6, 127.26, 128.23, 129.00, 129.74, 130.00,131.39, 134.42, 137.67, 137.97, 153.07, 160.33, 194.23 ppm.

6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine: A dry, 500 mL 3-neckround bottom flask is charged with a solution of 5.57 g (23.9 mmol) of2-formyl-6-naphthlypyridine and 4.81 g (27.1 mmol) of2,6-diisopropylaniline in 238 mL of anhydrous THF containing 3 Åmolecular sieves (6 g) and 80 mg of p-TsOH. The loading of the reactoris performed under N₂. The reactor is equipped with a condenser, an overhead mechanical stirrer and a thermocouple well. The mixture is heatedto reflux under N₂ for 12 h. After filtration and removal of thevolatile in vacuo, the crude, brown oil is triturated with hexanes. Theproduct is filtered off and rinsed with cold hexanes. The slightly offwhite solid weighes 6.42 g. No further purification is performed. mp142-144° C.

¹H NMR (CDCl₃) δ 1.3 (d, 12 H), 3.14 (m, 2H), 7.26 (m, 3H), 7.5-7.6 (m,5H), 7.75-7.8 (m, 3H), 8.02 (m 1H), 8.48 (m, 2H) ppm. ¹³C NMR (CDCl₃)23.96, 28.5, 119.93, 123.50, 124.93, 125.88, 125.94, 126.49, 127.04,127.24, 128.18, 128.94, 129.7, 131.58, 134.5, 137.56, 137.63, 138.34,148.93, 154.83, 159.66, 163.86 ppm.

(6-naphthyl-2-pyridyl)-N-(2,6-diisopropylphenyl)benzylamine: A 250 mL3-neck flask, equipped with mechanical stirrer and a N₂ sparge, ischarged with 6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine (6.19 mg,15.8 mmol) and 80 mL of anhydrous, degassed Et₂O. The solution is cooledto −78° C. while a solution of phenyllithium (13.15 mL of 1.8 M incyclohexane, 23.7 mmol) is added dropwise over 10 min. After warming toRT over 1 h. the solution is stirred at RT for 12 hours. The reaction isthen quenched with ˜50 mL of aq. NH₄Cl. The organic layer is separated,washed with brine and H₂O, then dried over Na₂SO₄. Using the BiotageChromatography system (column # FK0-1107-19073, 5% THF/95% hexanes), theproduct is isolated as a colorless oil. The chromatography is performedby dissolving the crude oil in 50 mL of hexanes. The purification isperformed in 2×˜25 mL batches, using half of the hexane stock solutionfor each run. 7.0 g of the oil is isolated (93% yield).

¹H NMR (CDCl₃) δ 0.90 (d, 12 H), 3.0 (m, 2H), 4.86 (s, 1H), 5.16 (s,1H), 7.00 (m, 3H), 7.1-7.6 (m, 12H), 7.8-7.88 (m, 2H), 7.91-7.99 (d, 1H)ppm. ¹³C NMR (CDCl₃) 24.58, 28.30, 70.02, 121.14, 123.62, 123.76,123.95, 125.71, 126.32, 126.55, 126.74, 127.45, 128.04, 128.74, 129.47,131.66, 134.49, 137.4, 138.95, 142.68, 143.02, 143.89, 159.36, 162.22ppm.

Catalyst G-(Nme₂)₃: The reaction is performed inside of a dry box. A 100mL round bottom flask is charged with Hf(Nme₂)₄ (2.5 g, 5.33 mmol), 30mL of pentane and a stir bar. The amine 1 is dissolve in 40 mL ofpentane then added to the stirring solution of Hf(Nme₂)₄. The mixture isstirred at ambient temperature for 16 h (overnight). The light yellowsolid is filtered off and rinsed with cold pentane. The dry weight ofthe powder is 2.45 g. A second crop is collected from the filtrateweighing 0.63 g. The overall yield is 74%.

¹H NMR (C₆D₆) δ 0.39 (d, 3 H, J=6.77 Hz), 1.36 (d, 3H, J=6.9 Hz), 1.65(d, 3H, J=6.68 Hz), 1.76 (d, 3H, J=6.78 Hz), 2.34 (br s, 6H), 2.80 (brs, 6H), 2.95 (br s, 6H), 3.42 (m, 1H, J=6.8 Hz), 3.78 (m, 1H, J=6.78Hz), 6.06 (s, 1H), 6.78 (m, 2H), 6.94 (m, 1H), 7.1-7.4 (m, 13H), 7.8 (m,2H) ppm.

Catalyst G: The reaction is performed inside of a dry box. A 100 mLround bottom flask is charged with 70 mL of pentane and 15 mL of a 2.0 Mtrimethyl aluminum in hexane solution. The solution is cooled to −40° C.The hafnium trisamide compound from the previous reaction (1.07, g 1.28mmol) is added in small portions over 5-10 minutes. Upon the addition, awhite gelatinous residue forms. After 45-60 min the reaction becomesyellow with a fine, yellow, powder precipitating from the mixture. Aftera total reaction time of 2.5 h the mixture is filtered and 615 mg ofCatalyst G is isolated as a bright, yellow powder. No furtherpurification is performed.

¹H NMR (C₆D₆) δ 0.51 (d, 3 H, J=6.73 Hz), 0.79 (s, 3H), 1.07 (s, 3H),1.28 (d, 3H, J=6.73 Hz), 1.53(m, 6H), 3.37 (m, 1H, J=6.75 Hz), 3.96 (m,1H, J=6.73 Hz), 6.05 (s, 1H), 6.50 (d, 1H, J=7.75 Hz), 6.92 (t, 1H,J=7.93 Hz), 7.1-7.59 (m, 12H), 7.6 (d, 1H), 7.8-8.0 (m, 2H), 8.3 (m,1H), 8.69 (d, 1H, J=7.65 Hz) ppm.

Synthesis of Catalyst H, FIG. 10H

To a solution of 9-bromophenanthrene (10.36 mg, 41 mmol) in 132 mL ofanhydrous, degassed Et₂O cooled to −40° C. is added under N₂ 27 mL (43.2mmol) of a 1.6 M solution of n-BuLi in hexanes. The solution is swirledto mix and allowed to react at −40° C. for 3 hours during whichcolorless crystals precipitated from solution. The9-phenanthrenyllithium is added as a slurry to a well-mixed solution of6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine (10.6 g, 27.04 mmol)in 130 mL of Et₂O cooled to −40° C. After warming to ambient temperatureover 1 h, the solution is stirred at ambient temperature for 2 hours.The reaction is then quenched with aq. NH₄Cl, and subjected to anaqueous/organic work-up. The organic washes are combined and dried overNa₂SO₄. Upon removal of the volatiles with rotary evaporation, theproduct precipitates from solution. The isolated solids are rinsed withcold hexanes. The material is vacuum dried at 70° C. using the housevacuum over night. The dried material is isolated as a white solid,weighing 12.3 g for a yield of 80%. A second crop is isolated weighing0.37 g. Mp 166-168° C.

¹H NMR (C₆D₆) δ 1.08 (dd, 12 H), 3.43 (m, 2H), 5.47 (m, 1H), 6.16 (d,1H), 7.0-7.8 (m, 14H), 8.2 (d, 1H), 8.5-8.6 (m, 4H), ppm. ¹³C NMR(CDCl₃) 24.68, 28.22, 68.87, 120.56, 122.89, 123.63, 123.73, 124.07,124.1, 125.5, 125.59, 126.24, 126.42, 126.52, 126.76, 126.83, 126.9,127.05, 127.14, 128.0, 128.55, 129.49, 129.55, 130.67, 130.71, 131.52,131.55, 132.24, 134.39, 137.57, 143.31, 159.1, 162 ppm.

Catalyst H-(Nme₂)₃: Inside of a dry box, six different teflon-screwcapped, glass pressure tube reactors are each charged with Hf(Nme₂)₄(1.55 g, 4.37 mmol, overall 9.3 g, 26.2 mmol), 10 mL of toluene and theligand isolated from the previous procedure above (2.1 g, 3.68 mmol,overall 12.6 g, 22.1 mmol). The tightly sealed reactors are removed fromthe dry box and placed in a heater block with the temperature set at125° C. The reactor tubes are heated overnight (˜16 h). The cooled tubesare taken into the dry box and the contents of the reactor tubes arecombined in a 500 mL round bottom flask. The flask is placed undervacuum to remove the dimethylamine and toluene. The light yellow/greensolid which is left is rinsed with ˜125 mL of cold pentane and filtered,yielding 13.6 g of a light yellow powder for a yield of 65%.

Catalyst H: The reaction is performed inside of a dry box. A 500 mL jaris charged with 250 mL of pentane and the hafnium amide isolated in theprocedure outlined immediately above (13.6 g, 15.5 mmol). The mixture iscooled to −40° C. To the stirring mixture is slowly added 70 mL of a 2.0M trimethyl aluminum (140 mmol) in hexane solution. After 3 h thereaction becomes yellow with a fine, powder precipitating from themixture. The mixture is then cooled to −40° C. and filtered. Theinitially collected product is rinsed with 2×60 mL of cold pentane.10.24 g Catalyst H is isolated (84% yield) with a purity of >99% by ¹HNMR.

Synthesis of Armeenium Borate[methylbis(hydrogenatedtallowalkyl)ammonium tetrakis (pentafluorophenyl)borate]

Armeenium borate can be prepared from ARMEEN® M2HT (available fromAkzo-Nobel), HCl, and Li [B(C₆F₅)₄] according to Example 2 of U.S. Pat.No. 5,919,983.

General 1 Gallon Continuous Solution Propylene/Ethylene

I. Copolymerization Procedure

Purified toluene solvent, ethylene, hydrogen, and propylene are suppliedto a 1 gallon reactor equipped with a jacket for temperature control andan internal thermocouple. The solvent feed to the reactor is measured bya mass-flow controller. A variable speed diaphragm pump controls thesolvent flow rate and increases the solvent pressure to the reactor. Thepropylene feed is measured by a mass flow meter and the flow iscontrolled by a variable speed diaphragm pump. At the discharge of thepump, a side stream is taken to provide flush flows for the catalystinjection line and the reactor agitator. The remaining solvent iscombined with ethylene and hydrogen and delivered to the reactor. Theethylene stream is measured with a mass flow meter and controlled with aResearch Control valve. A mass flow controller is used to deliverhydrogen into the ethylene stream at the outlet of the ethylene controlvalve. The temperature of the solvent/monomer is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters, and are combined with the catalystflush solvent. This stream enters the bottom of the reactor, but in adifferent port than the monomer stream. The reactor is run liquid-fullat 500 psig with vigorous stirring. The process flow is in from thebottom and out of the top. All exit lines from the reactor are steamtraced and insulated. Polymerization is stopped with the addition of asmall amount of water, and other additives and stabilizers can be addedat this point. The stream flows through a static mixer and a heatexchanger in order to heat the solvent/polymer mixture. The solvent andunreacted monomers are removed at reduced pressure, and the product isrecovered by extrusion using a devolatilizing extruder. The extrudedstrand is cooled under water and chopped into pellets. The operation ofthe reactor is controlled with a process control computer.

EXAMPLE 1 Propylene/Ethylene Polymerization

II. Using Metallocene Catalyst E (Comparative)

The general procedure for the 1 gallon continuous solutionpolymerization outlined above was employed. A catalyst solutioncontaining 2.6 ppm Zr from Catalyst E was prepared and added to a 4 Lcatalyst storage tank. This solution was combined in a continuous streamwith a continuous stream of a solution containing Armeeniumtetrakis(pentafluorophenyl)borate in toluene and a continuous stream ofa solution of PMAO-IP in toluene to give a ratio of total Ti:B:Al of1:1.2:30. The activated catalyst solution was fed continuously into thereactor at a rate sufficient to maintain the reactor temperature atapproximately 80 degrees C. and a polymer production rate ofapproximately 3 pounds an hour. The polymer solution was continuouslyremoved from the reactor exit and was contacted with a solutioncontaining 100 ppm of water for each part of the polymer solution, andpolymer stabilizers (i.e., 1000 ppm Irgaphos 168 and 1000 ppm Irganox1010 per part of the polymer). The resulting exit stream was mixed,heated in a heat exchanger, and the mixture was introduced into aseparator where the molten polymer was separated from the solvent andunreacted monomers. The resulting molten polymer was extruded andchopped into pellets after being cooled in a water bath. For thisexample, the propylene to ethylene ratio was 22.0. Product samples werecollected over 1 hour time periods, after which time the melt flow ratewas determined for each sample. FIG. 9 is a ¹³C NMR of ComparativeExample 1, and it demonstrates the absence of regio-error peaks in theregion around 15 ppm.

EXAMPLES 2-6

Examples 2-6 were conducted similar to Example 1 except as otherwisenoted in Tables 2-6-1 and 2-6-2 below. Catalyst E is listed forcomparative purposes. FIG. 8 is the ¹³C NMR sprectrum of thepropylene/ethylene copolymer product of Example 2. FIGS. 2A and 2B showa comparison of the DSC heating traces of the propylene/ethylenecopolymers of Comparative Example 1 and Example 2.

TABLE 2-6-1 Polymerization Conditions POLY Reactor SOLV C2 C3 H2 LBS/HRTEMP FLOW FLOW FLOW FLOW production Example DEG C. LB/HR LB/HR LB/HRSCCM rate 1 80.5 36.0 0.50 11.00 0 3.13 (com- parative) 2 80.5 33.0 0.206.00 20.8 3.47 3 80.1 26.0 0.10 6.00 14.1 3.09 4 79.9 26.0 0.20 6.0020.1 3.25 5 80.0 26.0 0.30 6.00 26.1 3.16 6 80.3 26.0 0.40 6.00 32.13.32

TABLE 2-6-2 Monomer conversion and activity catalyst efficiency C3/C2propylene ethylene concentration g metal Example Catalyst ratioconversion conversion ppm(metal) per g polymer 1 E 22.00 25.7% 64.8% 2.66,145,944 (comparative) 2 G 30.17 53.1% 99.1% 25.6 235,823 3 H 61.0748.7% 98.4% 55.0 225,666 4 H 30.34 49.7% 99.0% 55.0 259,545 5 H 20.1746.8% 98.6% 55.0 259,282 6 H 15.00 48.0% 98.7% 55.0 278,579

TABLE 2-6-3 Summary of Polymer Analysis Data DSC MFR Density Cryst. (%)Tg Tc, o Tc, p Example (g/10 min) (kg/dm3) from density (° C.) (° C.) (°C.) 1 72 0.8809 37.9 −26.1 52.3 47.6 2 1.7 0.8740 29.6 −24.8 59.0 49.3 32.2 0.8850 42.8 −10.0 76.6 64.5 4 2.3 0.8741 29.7 −23.2 50.8 41.6 5 20.8648 18.3 −27.1 30.4 10.9 6 2.0 0.8581 9.9 −29.6 — —

TABLE 2-6-4 Summary of Polymer Analysis Data cont'd ΔHc Cryst. (%) Tm, pTm, e ΔHf Cryst. (%) Example (J/g) (from Hc) (° C.) (° C.) (J/g) (fromHf) 1 40.8 24.7 91.9 114.3 52.1 31.6 2 27.1 16.4 64.5 128.9 38.0 23.0 345.0 27.3 102.2 145.7 65.3 39.6 4 30.6 18.5 67.4 145.6 42.9 26.0 5 8.75.3 50.0 119.4 13.0 7.9 6 — — — — — —

TABLE 2-6-5 Summary of Polymer Analysis Data cont'd Regio-errors 14–16Mn Mw Ethylene Ethylene ppm (kg/ (kg/ Example (wt %)* (mol %)* (mol %)*mol) mol) MWD 1 9.5 13.6 0.00 58.5 117.4 2.0 2 8.2 11.8 0.24 132.6 315.72.4 3 5.6 8.2 0.46 146.0 318.3 2.2 4 8.2 11.8 0.34 138.5 305.7 2.2 511.1 15.8 0.35 6 13.2 18.6 0.37 127.5 306.8 2.4 *determined by NMR

TABLE 2-6-6 Summary of Polmer Analysis Data cont'd Example % mm* % mr* %rr* 1 98.55 0 1.45 2 98.23 1.09 5.68 3 94.3 2.21 3.43 4 96.37 0 3.63 595.3 0.0 4.66 6 95.17 0 4.83 *corrected PPE + EPE

EXAMPLES 7-8 Homopolymerization of Propylene Using Catalyst B and C

Examples 7-8 were conducted similar to Example 1 without ethylene. Theprocedure was similar to Example 1 with exceptions noted in Tables 7-8-1and 7-8-2 below. FIG. 6 shows the ¹³C NMR spectrum of the propylenehomopolymer product of Example 7 prepared using catalyst G. FIG. 7 showsthe ¹³C NMR spectrum of the propylene homopolymer product of Example 8prepared using catalyst H. Both spectra show a high degree ofisotacticity, and the expanded Y-axis scale of FIG. 7 relative to FIG. 6shows more clearly the regio-error peaks. FIGS. 11A-B show the DSCheating and cooling traces of the propylene homopolymer of Example 8.

TABLE 7-8-1 Reactor Conditions and Catalyst Activity Reactor SOLV C3 H2POLY catalyst efficiency TEMP FLOW FLOW FLOW LBS/HR propyleneconcentration g metal Example DEG C. LB/HR LB/HR SCCM WEIGHED Catalystconversion ppm(metal) per g polymer 7 99.8 33.1 6.00 1.9 2.30 G 38.3%25.6 111,607 8 100.3 26.0 6.00 2.6 2.57 H 42.8% 32.5 100,987

TABLE 7-8-2 Polymer Analysis DSC MFR Density Cryst. (%) Tg Tc, o Tc, pMn Mw Example (g/10 min) (kg/dm3) from density (° C.) (° C.) (° C.)(kg/mol) (kg/mol) MWD 7 1.9 0.8995 59.7 −6.0 104.2 100.4 114.6 350.8 2.78 2.5 0.9021 62.7 −8.1 105.7 103.3 125.5 334.0 2.7

TABLE 7-8-3 Polymer Analysis Continued ΔHc Cryst. (%) Tm, p Tm, e ΔHfCryst. (%) Regio-errors Example (J/g) (from Hc) (° C.) (° C.) (J/g)(from Hf) 14–16 ppm(mol %)* % mm** % mr** % rr** 7 76.9 46.6 139.7 153.593.7 56.8 2.69 92.12 5.79 2.08 8 83.6 50.7 144.5 158.2 100.6 61.0 2.3693.93 4.45 1.62 *determined by NMR **corrected PPE + EPE

EXAMPLE 9

This example demonstrates the calculation of B values for certain of theExamples disclosed herein. The polymer from Comparative Example 1 isanalyzed as follows. The data was collected using a Varian UNITY Plus400 MHz NMR spectrometer, corresponding to a ¹³C resonance frequency of100.4 MHz. Acquisition parameters were selected to ensure quantitative¹³C data acquisition in the presence of the relaxation agent. The datawas acquired using gated ¹H decoupling, 4000 transients per data file, a7 sec pulse repetition delay, spectral width of 24,200 Hz and a filesize of 32K data points, with the probe head heated to 130° C. Thesample was prepared by adding approximately 3 mL of a 50/50 mixture oftetrachloroethane-d2/orthodichlorobenzene that is 0.025M in chromiumacetylacetonate (relaxation agent) to 0.4 g sample in a 10 mm NMR tube.The headspace of the tube was purged of oxygen by displacement with purenitrogen. The sample was dissolved and homogenized by heating the tubeand its contents to 150° C., with periodic refluxing initiated by heatgun.

Following data collection, the chemical shifts were internallyreferenced to the mmmm pentad at 21.90 ppm.

For propylene/ethylene copolymers, the following procedure is used tocalculate the percent ethylene in the polymer. Integral regions aredetermined as follows:

TABLE 9-1 Integral Regions for Calculating % Ethylene Region designationPpm Integral area A 44–49 259.7 B 36–39 73.8 C 32.8–34   7.72 P31.0–30.8 64.78 Q Peak at 30.4 4.58 R Peak at 30 4.4 F 28.0–29.7 233.1 G  26–28.3 15.25 H 24–26 27.99 I 19–23 303.1

-   Region D is calculated as follows: D=P×(G×Q)/2.-   Region E is calculated as follows: E=R+Q+(G×Q)/2.-   The triads are calculated as follows:

TABLE 9-2 Traid Calculation PPP = (F + A − 0.5D)/2 PPE = D EPE = C EEE =(E − 0.5G)/2 PEE = G PEP = H Moles P = (B + 2A)/2 Moles E = (E + G +0.5B + H)/2

-   For this example, the mole % ethylene is calculated to be 13.6 mole    %.-   For this example, the triad mole fractions are calculated to be as    follows:

TABLE 9-3 Triad Mole Calculation PPP = 0.6706 PPE = 0.1722 EPE = 0.0224EEE = 0.0097 PEE = 0.0442 EPE = 0.0811

-   From this, the B value is calculated to be    (0.172+0.022+0.044+0.081)/2(0.136×0.864)=1.36-   In a similar manner, the B values for the following examples are    calculated to be:

TABLE 9-4 B-Value Calculation Example B Value Comparative 1 1.36 2 1.683 1.7 4 1.78 6 1.7

EXAMPLE 10

Table 10 is a summary showing the skewness index, S_(ix), for inventiveand prior art samples. All of the samples were prepared and measured asdescribed in Table C in the Description of the Preferred Embodiments andentitled Parameters Used for TREF. The copolymers of the invention havea skewness index greater than about (−1.2). The results from Table 10are represented graphically in FIG. 12.

The inventive examples show unusual and unexpected results when examinedby TREF. The distributions tend to cover a large elution temperaturerange while at the same time giving a prominent, narrow peak. Inaddition, over a wide range of ethylene incorporation, the peaktemperature, T_(Max), is near 60° C. to 65° C. In the prior art, forsimilar levels of ethylene incorporation, this peak moves to higherelution temperatures with lower ethylene incorporation.

For conventional metallocene catalysts the approximate relationship ofthe mole fraction of propylene, X_(p), to the TREF elution temperaturefor the peak maximum, T_(Max), is given by the following equation:Log_(e)(X _(p))=+289/(273+T _(max))+0.74

For the inventive copolymers, the natural log of the mole fraction ofpropylene, LnP, is greater than that of the conventional metallocenes,as shown in this equation:LnP>289/(273+T _(max))+0.75

TABLE 10 Summary of Skewness Index Results Ethylene Elution TemperatureCatalyst Content of Peak Maximum Inventive Inventive Type (Mole %) (°C.) S_(ix) Sample 10-1 Catalyst H 8.2 61.4 0.935 Sample 10-2 Catalyst J8.9 60.8 −0.697 Sample 10-3 Catalyst J 8.5 61.4 −0.642 Sample 10-4Catalyst J 7.6 65.0 0.830 Sample 10-5 Catalyst J 7.6 65.0 0.972 Sample10-6 Catalyst J 8.6 61.4 0.804 Sample 10-7 Catalyst J 9.6 60.2 −0.620Sample 10-8 Catalyst J 12.4 60.2 0.921 Sample 10-9 Catalyst J 8.6 60.8−0.434 Sample 10-10 Catalyst J 8.6 62.0 1.148 Sample 10-11 Catalyst H57.8 1.452 Sample 10-12 Catalyst J 78.2 1.006 Sample 10-13 Catalyst H4.4 80.0 −1.021 Sample 10-14 Catalyst E 7.6 80.6 −1.388 Sample 10-15Catalyst E 10.0 70.4 −1.278 Sample 10-16 Catalyst F 10.7 66.2 −1.318Sample 17-17 Catalyst F 11.1 69.2 −1.296 Sample 17-18 Catalyst E 10.665.6 −1.266

EXAMPLE 11

DSC analysis shows that propylene/ethylene copolymers produced by asolution polymerization process using a nonmetallocene, metal-centered,pyridal-amine ligand catalyst have melting behavior that differs insurprising ways from propylene/ethylene copolymers produced bymetallocene polymerization processes that are known in the art. Thedifferent melting behavior of these copolymers compared to that ofcopolymers that are known in the art not only demonstrates the noveltyof these materials, but also can be used to infer certain advantages ofthese materials for some applications. The novel aspects of the meltingbehavior of these copolymers and their associated utility are discussedbelow, after first describing the DSC analysis method.

Any volatile materials (e.g., solvent or monomer) are removed from thepolymer prior to DSC analysis. A small amount of polymer, typically fiveto fifteen milligrams, is accurately weighed into an aluminum DSC panwith lid. Either hermetic or standard type pans are suitable. The pancontaining the sample is then placed on one side of the DSC cell, withan empty pan with lid placed on the reference side of the DSC cell. TheDSC cell is then closed, with a slow purge of nitrogen gas through thecell during the test. Then the sample is subjected to a programmedtemperature sequence that typically has both isothermal segments andsegments where the temperature is programmed to increase or decrease ata constant rate. Results that are presented here were all obtained usingheat-flux type DSC instruments manufactured by TA Instruments (e.g.,Model 2910 DSC). The measurement principles underlying heat-flux DSC aredescribed on page 16 of Turi, ibid. The primary signals generated bysuch instruments are temperature (units: ° C.) and differential heatflow (units: watts) into or out of the sample (i.e., relative to thereference) as a function of elapsed time. Melting is endothermic andinvolves excess heat flow into the sample relative to the reference,whereas crystallization is exothermic and involves excess heat flow outof the sample. These instruments are calibrated using indium and othernarrow-melting standards. Calibration ensures that the temperature scaleis correct and for the proper correction of unavoidable heat losses.

Temperature programs for DSC analysis of semi-crystalline polymersinvolve several steps. Although the temperature programs used togenerate the data presented here differed in some details, the criticalsteps were maintained constant throughout. The first step is an initialheating to a temperature sufficient to completely melt the sample; forpolypropylene homopolymers and copolymers, this is 210° C. or higher.This first step also helps insure excellent thermal contact of thepolymer sample with the pan. Although details of this first stepdiffered for data presented here—for example, the rate of heating, theupper temperature, and the hold time at the upper temperature—in allcases the choices were sufficient to achieve the principal objectives ofthis step, of bringing all samples to a common completely meltedstarting point with good thermal contact. The second step involvescooling at a constant rate of 10° C./min from an upper temperature of atleast 210° C. to a lower temperature of 0° C. or less. The lowertemperature is chosen to be at or slightly below the glass transitiontemperature of the particular propylene polymer. The rate ofcrystallization becomes very slow at the glass transition temperature;hence, additional cooling will have little effect on the extent ofcrystallization. This second step serves to provide a standardcrystallization condition, prior to examining subsequent meltingbehavior. After a brief hold at this lower temperature limit, typicallyone to three minutes, the third step is commenced. The third stepinvolves heating the sample from a temperature of 0° C. or lower (i.e.,the final temperature of the previous step) to 210° C. or higher at aconstant rate of 10° C./min. This third step serves to provide astandard melting condition, as preceded by a standard crystallizationcondition. All the melting behavior results presented here were obtainedfrom this third step, that is, from the second melting of the sample.

The output data from DSC consists of time (sec), temperature (° C.), andheat flow (watts). Subsequent steps in the analysis of meltingendotherms are as follows. First, the heat flow is divided by the samplemass to give specific heat flow (units: W/g). Second, a baseline isconstructed and subtracted from the specific heat flow to givebaseline-subtracted heat flow. For the analyses presented here, astraight-line baseline is used. The lower temperature limit for thebaseline is chosen as a point on the high temperature side of the glasstransition. The upper temperature limit for the baseline is chosen as atemperature about 5-10° C. above the completion of the meltingendotherm. Although a straight-line baseline is theoretically not exact,it offers greater ease and consistency of analysis, and the errorintroduced is relatively minor for samples with specific heats ofmelting of about 15-20 Joules per gram or higher. Employing astraight-line baseline in lieu of a more theoretically correct baselinedoes not substantively affect any of the results or conclusionspresented below, although the fine details of the results would beexpected to change with a different prescription of the instrumentalbaseline.

There are a number of quantities that can be extracted from DSC meltingdata. Quantities that are particularly useful in demonstratingdifferences or similarities among different polymers are: (1) the peakmelting temperature, T_(max) (° C.), which is the temperature at whichthe baseline-subtracted heat flow is a maximum (here the convention isthat heat flow into the sample is positive); (2) the specific heat ofmelting, Δh_(m) (J/g), which is the area under the melting endothermobtained by integrating the baseline-subtracted heat flow (dq/dt) (W/g)versus time between the baseline limits; (3) the specific heat flow(dq/dt)_(max) (W/g) at the peak melting temperature; (4) the peakspecific heat flow normalized by the specific heat of melting,{(dq/dt)_(max)/Δh_(m)} (sec⁻¹); (5) the first moment T₁ of the meltingendotherm, defined and calculated as described below; (6) the varianceV₁ (° C.²) of the melting endotherm relative to the first moment T₁,defined and calculated as described below; and (7) the square root ofthe variance, V₁ ^(1/2) (° C.), which is one measure of the breadth ofthe melting endotherm.

Treatment of the melting endotherm as a distribution is a useful way toquantify its breadth. The quantity that is distributed as a function oftemperature is the baseline-subtracted heat flow (dq/dt). That this isalso a distribution of temperature is made explicit using the calculuschain rule, (dq/dt)=(dq/dT)(dT/dt) where (dT/dt) is the heating rate.The standard definition of the first moment T₁ of this distribution isgiven by the following equation, where the integrations are carried outbetween the baseline limits. All integrations are most reliablyperformed as (dq/dt) versus time, as opposed to the alternative (dq/dT)versus temperature. In the following equation, (dq/dt) and T are thespecific heat flow and temperature at time t.

$T_{1} = \frac{\int{{T \cdot ( {{\mathbb{d}q}/{\mathbb{d}t}} )}{\mathbb{d}t}}}{\int{( {{\mathbb{d}q}/{\mathbb{d}t}} ){\mathbb{d}t}}}$The variance V₁ relative to the first moment is then standardly definedas:

$V_{1} = \frac{\int{{( {T - T_{1}} )^{2} \cdot ( {{\mathbb{d}q}/{\mathbb{d}t}} )}{\mathbb{d}t}}}{\int{( {{\mathbb{d}q}/{\mathbb{d}t}} ){\mathbb{d}t}}}$Both V₁ and V₁ ^(1/2) are measures of the breadth of the meltingendotherm.

Results of DSC analyses of both inventive and comparative polymers areshown in Table 11-1. All the samples are propylene/ethylene copolymers,with the exception of Samples 1-4 and 17 which are homopolymers.Polymers 1-16 were made using Catalyst H in a solution process. Polymers17-27 were made with Catalyst E in a solution process. An idea of theprecision of the experimental method plus the data analysis procedure isprovided by replicates (polymers 17, 20, and 22) and by the consistencyof results for sets of polymers that were synthesized under nearlyidentical conditions (polymers 1-4, 7-9, 10-12, and 13-16).

Differences in melting behavior are most easily seen with the aid offigures. FIG. 13 compares the melting endotherms of Samples 8 and 22a.These two propylene/ethylene copolymers have nearly equivalent heats ofmelting and mole percent ethylene contents, about 71 J/g and 8 mole %.However, despite these similarities, the melting behavior of theinventive copolymer (Sample 8) is surprisingly different than that ofthe comparative copolymer (Sample 22a). The melting endotherm of Sample8 is shifted towards lower temperatures and significantly broadened,when comparing at equivalent heat of melting. These changes in meltingbehavior are unique to and characteristic of the copolymers of thisinvention.

Comparison at equivalent heats of melting is particularly meaningful andrelevant. This is because equivalent heats of melting impliesapproximately equal levels of crystallinity, which in turn implies thatthe room temperature moduli should be similar. Therefore, at a givenmodulus or stiffness, the copolymers of this invention possess usefullybroadened melting ranges compared to typical non-inventive copolymers.

FIGS. 18-22, which are derived from the results in Table 11-1, furtherhighlight the differences in melting behavior for the copolymers of thisinvention compared to typical copolymers. For all five of these figures,quantities are plotted as functions of the heat of melting, which asdescribed above is an especially meaningful and relevant basis formaking intercomparisons and inferring utility. For these plots, datahave broken into two series based on the catalyst type used to make thepolymer, either metallocene or nonmetallocene type.

FIG. 14 demonstrates how the peak melting temperature is shifted towardslower temperature for the copolymers of this invention. All the changesin melting behavior, of which this shift in peak melting temperature isbut one example, imply that there are differences in the crystallinestructure at the level of crystal lamellae or other type of primarycrystalline elements. In turn, such differences in crystalline structurecan most reasonably be attributed to differences in microstructure, forexample, the different type of mis-insertion errors or the higher Bvalues that characterize the polymers of this invention. Regardless ofthe exact nature of the microstructural features that give rise to thechanges in melting behavior, the changes are in and of themselvesevidence that the copolymers of this invention are novel compositions.

FIG. 15 which shows a plot of the temperature T_(1% c) at which there isapproximately 1% residual crystallinity, demonstrates another surprisingaspect of the melting behavior of the copolymers of this invention. Thefactor that is used to convert specific heat of melting into nominalweight % crystallinity is 165 J/g=100 weight % crystallinity. (Use of adifferent conversion factor could change details of the results but notsubstantive conclusions.) With this conversion factor, the totalcrystallinity of a sample (units: weight % crystallinity) is calculatedas 100% times Δh_(m) divided by 165 J/g. And, with this conversionfactor, 1% residual crystallinity corresponds to 1.65 J/g. Therefore,T_(1% c) is defined as the upper limit for partial integration of themelting endotherm such that Δh_(m) minus the partial integral equals1.65 J/g, where the same lower limit and baseline are used for thispartial integration as for the complete integration. Surprisingly, forthe copolymers catalyzed with a nonmetallocene, metal-centered,heteroaryl ligand catalyst, as compared to metallocene-catalyzedcopolymers, this 1% residual crystallinity temperature shifts downwardless rapidly with increase in ethylene level (i.e., with decrease in theheat of melting). This behavior of T_(1% c) is similar to that of thefinal temperature of melting T_(me).

FIG. 16, which shows the variance relative to the first moment of themelting endotherm as a function of the heat of melting, demonstratesdirectly the greater breadth of the melting endotherm for the copolymersof this invention.

FIG. 17, which shows the maximum heat flow normalized by the heat ofmelting as a function of the heat of melting, further demonstrates thebroadening of the melting endotherm. This is because, at equivalent heatof melting, a lower peak value implies that the distribution must bebroadened to give the same area. Roughly approximating the shape ofthese melting curves as a triangle, for which the area is given by theformula one-half times the base times the height, then b1/b2=h2/h1. Theinventive copolymers show as much as a four-fold decrease in height,implying a significant increase in breadth.

FIG. 18 illustrates a useful aspect of the broader melting range of theinventive polymers, namely that the rate at which the last portion ofcrystallinity disappears (units: weight % crystallinity per ° C.) issignificantly lower than for metallocene polymers.

The data in Table 11-2 demonstrate in practical terms the utility ofthis broadening of the melting endotherm. Entries in Table 11-2illustrate: (1) the extent to which a greater fraction of melting occursat lower temperatures, which is important for heat seal and bondingapplications, and which is greater for the inventive copolymers; and (2)the extent to which crystallinity remains at higher temperatures and therate at which the final portion of crystallinity disappears, which canbe important for fabrication operations such as thermoforming, foaming,blow molding, and the like, both of which are greater for the inventivecopolymers.

TABLE 11-1 Melting Results from DSC ethylene Δh_(m) T_(max) T₁(dq/dt)_(max)/Δh_(m) V₁ T_(1% c) Sample* (mole %) (J/g) (° C.) (° C.)(sec⁻¹) (° C.²) (° C.) R_(f) (**) 11-1-1 0.0 90.4 139.0 123.5 0.0109 416143.0 1.60 11-1-2 0.0 94.3 138.8 122.2 0.0105 505 143.1 1.54 11-1-3 0.094.0 139.4 122.4 0.0105 505 143.3 1.60 11-1-4 0.0 95.9 139.5 121.40.0102 576 143.4 1.60 11-1-5 1.5 92.4 138.2 118.4 0.0105 630 142.0 1.4811-1-6 4.3 85.0 120.7 99.2 0.0045 716 135.0 0.40 11-1-7 8.2 67.5 85.983.8 0.0023 909 139.7 0.19 11-1-8 8.2 71.2 93.0 84.4 0.0025 835 137.50.19 11-1-9 8.2 74.6 108.2 87.0 0.0029 790 134.6 0.23 11-1-10 11.8 51.671.7 69.3 0.0024 790 124.4 0.14 11-1-11 11.8 52.5 74.8 69.4 0.0025 781123.7 0.14 11-1-12 11.8 51.9 73.9 69.4 0.0025 802 124.3 0.14 11-1-1315.8 24.0 55.2 66.7 0.0031 667 112.0 0.10 11-1-14 15.8 28.7 55.2 66.30.0026 795 118.0 0.10 11-1-15 15.8 27.6 55.6 66.0 0.0026 783 116.4 0.1011-1-16 15.8 26.9 55.2 66.4 0.0026 769 115.7 0.10 11-1-17a 0.0 120.7160.3 145.3 0.0104 457 165.9 1.43 11-1-17b 0.0 123.9 159.8 144.5 0.0105486 165.2 1.54 11-1-18 — 90.3 140.6 125.0 0.0076 419 146.1 1.21 11-1-19— 91.3 139.0 123.9 0.0068 374 145.5 1.05 11-1-20a 4.2 110.2 137.7 121.80.0094 337 144.3 0.95 11-1-20b 4.2 96.5 137.9 121.1 0.0100 451 142.71.38 11-1-21 — 94.6 136.7 120.3 0.0086 385 140.5 1.43 11-1-22a 8.0 71.4117.5 105.8 0.0081 197 124.8 0.74 11-1-22b 8.0 69.7 117.0 103.4 0.0080271 122.8 1.00 11-1-23 — 70.1 110.3 91.0 0.0062 512 115.9 0.95 11-1-24 —55.9 97.0 78.7 0.0052 436 103.9 0.67 11-1-25 — 19.8 63.0 61.1 0.0044 18880.1 0.25 11-1-26 — 18.2 56.6 58.8 0.0049 158 75.3 0.27 *Samples 11-1-1to -4 made with catalyst G, samples -5 to -16 with catalyst H, and -17to -24 with catalyst E. (**) Units for R_(f): weight % crystallinity per° C.

TABLE 11-2 Broadening of the Melting Endotherm Starting FractionFraction Fraction Fraction Crystallinity Melted Melted RemainingRemaining Sample (weight %) at T₁ − 30° C. at T₁ − 20° C. at T₁ + 20° C.at T₁ + 30° C. 11-2-8 (inventive) 43.2 0.153 0.229 0.249 0.134 11-2-22a(comparative) 43.3 0.040 0.112 0.019 0.004 11-2-11 (inventive) 31.80.143 0.235 0.221 0.131 11-2-25 (comparative) 33.9 0.103 0.170 0.1270.009

EXAMPLE 12

Table 12 reports the haze, blooming, flex modulus andductile-to-brittle-transition temperature (DBTT) performance of a numberof different blends comprising a crystalline polypropylene matrix and animpact modifying polymer dispersed phase. The composition of the blendcomponents and the protocols for preparing and testing the blends arereported after Table 12.

The data in Table 12 shows that high MFR elastomers do not bloom if theyare crystalline (compare Samples 12-2/3 with 12-4/5/6); low MFRelastomers do not bloom (compare Samples 12-2/3 with 12-1 and 12-7/8)and the haze of the blend is even lower if the elastomer is alsocrystalline (compare Samples 12-2/3 with 12-7/8); and high MFRelastomers do not bloom if they are crystalline (compare Samples12-9/10/11 with 12-12/13/14/15/16/17. The difference between bloomingand nonblooming reported in Table 12 occurs between 0.030-0.040 mg/3 g.The measurement of blooming was made 48 hours after the blends wereinjection molded.

TABLE 12 Ratio (wt) Flex Sample Matrix/ Haze Blooming Blooming ModulusDBTT ° C., Number Matrix Elastomer Elastomer (%) mg/3 g Visual Kpsi Dyn12-1 Profax SR256M P/E via CGC Catalyst 90/10 28 0.030 Non-blooming 113−2 (16 mol % E, 2 MFR, 0% crystallinity) 12-2 Profax SR256M P/E via CGCCatalyst 90/10 25 0.100 Blooming 105 −2 (30 mol % E, 61 MFR, 0%crystallinity) 12-3 Profax SR256M P/E via CGC Catalyst 90/10 22 0.076Blooming 113 −10 (40 mol % E, 87 MFR, 0% crystallinity) 12-4 ProfaxSR256M P/E via Metallocene Catalyst 90/10 13 0.017 Non-blooming 151 5(10.6 mol % E, 186 MFR, 40% crystallinity) 12-5 Profax SR256M P/E viaMetallocene Catalyst 90/10 13 0.019 Non-blooming 141 3 (10.6 mol % E, 33MFR, 37% crystallinity) 12-6 Profax SR256M P/E via Metallocene Catalyst90/10 14 0.003 Non-blooming 147 8 (10.6 mol % E, 21 MFR, 38%crystallinity) 12-7 Profax SR256M P/E via Catalyst H 90/10 12 0.023Non-blooming 125 −1 (15.8 mol % E., 2MFR, 16% crystallinity) 12-8 ProfaxSR256M P/E via Catalyst H 90/10 15 0.024 Non-blooming 120 −5 (18.6 mol %E, 2MFR, 2% crystallinity) 12-9 H308-02Z P/E via Catalyst H 85/15 200.017 Non-blooming 147 10 (14.3 mol % E, 25 MFR, 21% crystallinity)12-10 H314-02Z P/E via Catalyst H 85/15 19 0.025 Non-blooming 161 12(14.3 mol % E, 75 MFR, 20% crystallinity) 12-11 H308-02Z P/E viaCatalyst H 85/15 17 0.016 Non-blooming 176 20 (11.5 mol % E, 25 MFR, 31%crystallinity) 12-12 H308-02Z P/E via Catalyst H 85/15 28 0.045 Blooming158 −2 (30 mol % E, 25 MFR, 0% crystallinity) 12-13 H308-02Z P/E viaCatalyst H 85/15 27 0.058 Blooming 155 −5 (30 mol % E, 75 MFR, 0%crystallinity) 12-14 H308-02Z P/E via CGC Catalyst 85/15 25 0.040Blooming 140 10 (16 mol % E, 25 MFR, 0% crystallinity) 12-15 H308-02ZP/E via CGC Catalyst 85/15 33 0.068 Blooming 141 10 (16 mol % E, 75 MFR,0% crystallinity) 12-16 H308-02Z P/E via CGC Catalyst 85/15 24 0.060Blooming 137 10 (4 mol % E, 25 MFR, 0% crystallinity) 12-17 H308-02Z P/Evia CGC Catalyst 85/15 38 0.086 Blooming 138 10 (4 mol % E, 75 MFR, 0%crystallinity)The blends identified in Table 12 were prepared using the followingmaterials:

-   -   Profax SR256M, a 3 wt % ethylene random copolymer with MFR=2        g/10 min (MFR is Melt Flow Rate measured according to ASTM D1248        with a 2.16 kg weight at 230° C.).    -   Dow Polypropylene Resin H308-02Z, a 0.5 wt % ethylene random        copolymer with MFR=2 g/10 min, and nucleated with 2000 ppm NA-11        (methylene-bis-(4,6-di-tert-butylphenyl)phosphate sodium salt        manufactured by Asahi Denka).

Blends of SR256M and elastomer were prepared in a 90/10 weight ratio,and blends of H308-02Z and elastomer were prepared in a 85/15 weightratio. The blending procedure was the following:

-   -   Either 1) the pellets of the desired composition were tumble        blended for 3 minutes in the presence of Irganox B225 in a        sufficient amount to result in 1000 ppm in the final        composition; or 2) the desired composition was mixed using a        Kobelco batch mixer at 165-175° C. for 3 minutes at a torque of        16-22%.    -   The resulting blended compositions were extruded on a 30 mm        Werner & Plfeiderer extruder with a temperature profile of        100/160/180/190/200° C., a screw speed of 300 rpm and a feed        rate of 25 lbs/hr, resulting in a torque of 50%.    -   The resulting blends were injection molded and analyzed for haze        (ASTM D1003). Blooming resistance is qualitatively measured by        visual inspection of injection molded haze plaques after aging        for two weeks; blooming appears as a milky layer on the surface        that can be scratched or washed off.        Surface Wash of Polypropylene Samples

In order to understand the amount of material that was blooming to thesurface, a consistent procedure was used to conduct a surface wash ofthe polypropylene material:

One-millimeter polypropylene plaques were injection molded as hazeplaques according to ASTM D-1003. Three grams (+/−0.002) of the pressedplaque was added to a clean 40-milliliter glass vial. 10 milliliters ofchloroform was added to the vial and the vial was swirled for 3 minutes.After 3 minutes, the chloroform was quickly decanted into a clean20-milliliter glass vial (leaving the plaque behind). The 20-milliliterglass vial containing the chloroform solution was then set on a hotplateat 58 degrees Celsius for approximately 2 hours in a fume hood toevaporate the chloroform. The samples were inspected visually to ensurecomplete evaporation. After evaporation, 1.6 milliliters+/−0.02milliliter of 1,2,4-trichlorobenzene was then added to the 20-millilitervial and the vial was swirled gently. The solution was allowed toequilibrate for 10 minutes on the hot plate set at 160 degrees Celsius.The 1,2,4-trichlorobenzene solution in the 20-milliliter vial was thendecanted into a 2-milliliter glass vial for injection onto thechromatographic system.

Description of Conventional GPC System for Polypropylene Analysis

The chromatographic system consisted of a Polymer Laboratories ModelPL-210 high-temperature chromatograph. The column and carouselcompartments were operated at 160° C. The carousel warm-zone was set to145° C. The columns used were 4 Polymer Laboratories 20-micron Mixed-Acolumns. The solvent used was 1,2,4 trichlorobenzene. The samples wereprepared at a concentration of 0.15 grams of polymer in 50 millilitersof solvent. The solvent used to prepare the samples contained 200 ppm ofbutylated hydroxytoluene (BHT). Samples were prepared by agitatinglightly for 2 hours at 160° C. The injection volume used was 100microliters and the flow rate was 1.0 milliliters/minute.

Calibration of the GPC column set was performed with narrow molecularweight distribution polystyrene standards purchased from PolymerLaboratories. The polystyrene standard peak molecular weights wereconverted to polypropylene molecular weights by way of the Mark-Houwinkcoefficients according to the following equation:

$M_{polyolefin} = \lbrack \frac{k_{{polystyrene}\;}M_{polstyrene}^{a_{polystyrene} + 1}}{k_{polyolefin}} \rbrack^{\frac{1}{a_{polyalefin} + 1}}$where:Log K polystyrene=−3.900 apolystyrene=0.702 andLog K polyolefin=−3.721 apolyolefin=0.725Polypropylene equivalent molecular weight calculations using theMark-Houwink ratioing method were performed using Viscotek TriSECsoftware Version 3.0.Numerical Quantification of GPC Chromatogram into Mass Recovery

The refractometer area was obtained by integrating an internalpolypropylene sample of 239,000 molecular weight. The refractometer areawas used to calculate a “mass constant” for the refractive indexdetector (converting the refractometer signal in mV to concentrationunits) for the polypropylene unknown samples using the equation listedbelow:

${{Mass}\mspace{14mu}{Constant}} = \frac{\sum\limits_{i = 0}^{npts}{{RI}_{i}*{FlowRate}*{Collection}\mspace{14mu}{Rate}}}{{Injection}\mspace{14mu}{Volume}*{Concentration}*{{\mathbb{d}n}/{\mathbb{d}\; c}}}$where the mass constant is in mV/RIU, RI is in mV, flowrate is inml/min, collection rate is in min/pt, injection volume is in ml,concentration is in mg/ml, dn/dc is in RIU×ml/mg.

The mass recovered for a specific sample is then obtained by rearrangingthe previous equation in the form shown below:

${{Mass}\mspace{14mu}{Recovered}} = {{{Injection}\mspace{14mu}{Volume}*{Concentration}} = \frac{\sum\limits_{i = 0}^{npts}{{RI}_{i}*{FlowRate}*{Collection}\mspace{14mu}{Rate}}}{{Mass}\mspace{14mu}{Constant}*{{\mathbb{d}n}/{\mathbb{d}\; c}}}}$The mass recovery was chosen as the material that was detected by therefractometer containing a substantial molecular weight (>1,600MW basedon the Conventional GPC calibration).Conversion of GPC Mass Recovery into Percent of Polypropylene MassBlooming from Film Material

-   1) The mass recovery of the material was divided by the known    injection volume (0.100+/−0.003 milliliters: verified by filling the    loop with water, weighing, and cutting to a precise length) of the    chromatographic material to convert it to concentration units.-   2) The mass of film (3000 milligrams) was divided by the 1.6    milliliters of 1,2,4 trichlorobenzene to produce the total    concentration of film material that had the potential to dissolve.-   3) The result of step (1) was divided by the result of step (2) and    multiplied by 100 to yield the percent mass blooming from the film    material.

EXAMPLE 13

The blends listed in Table 13 below were prepared using the followingmaterials:

-   -   Profax SR256M is described in Example 12.    -   A propylene-ethylene elastomer prepared via CGC catalysis in a        solution process, containing 16 mol% ethylene with MFR=2 g/10        min.    -   A propylene-ethylene elastomer prepared via Catalyst H catalysis        in a solution process, containing 16 mol% ethylene with MFR=2        g/10 min.

Blends of SR256M and the Catalyst H catalyzed elastomer were prepared ina 90/10 and a 80/20 weight ratio. Blends of SR256M and the CGC catalyzedelastomer were also prepared in a 90/10 and a 80/20 weight ratio. Theblending procedure was as follows:

-   -   the pellets of the desired composition were tumble blended for 3        minutes in the presence of Irganox B225 in a sufficient amount        to result in 1000 ppm in the final composition    -   the tumble blended compositions were extruded on a 30 mm        Werner&Plfeiderer extruder with a temperature profile of        100/160/180/190/200° C., a screw speed of 300 rpm and a feed        rate of 25 lb/hr, resulting in a torque of 50%.    -   The resulting blends were injection molded and analyzed for haze        (ASTM D1003), flexural modulus (ASTM 0790-970 and        ductile-to-brittle-transition temperature (DBTT) by Dynatup        impact (ASTM D3763-97a).

TABLE 13 Ratio (wt) Sam- Ma- ple trix/ DBTT Flex. Num- Elas- (° C., Mod.Haze ber Matrix Elastomer tomer Dyn) (kpsi) (%) 21-1 Profax P/E viaCatalyst H 90/10 0 121 17 SR256M (16 mol % E, 2MFR) 21-2 Profax P/E viaCGC Catalyst 90/10 −2 113 28 SR256M (16 mol % E, 2MFR) 21-3 Profax P/Evia Catalyst H 80/20 −5 90 14 SR256M (16 mol % E, 2 MFR) 21-4 Profax P/Evia CGC Catalyst 80/20 −10 84 34 SR256M (16 mol % E, 2 MFR)

Blend 13-1 shows much lower haze compared to blend 13-2 and slightlybetter modulus; the same is true for blend 13-3 versus blend 13-4(comparison of blends containing the same rubber content, and containingrubbers that have the same ethylene content but were prepared viadifferent catalysis).

Also, blend 13-3 shows better haze and better impact than blend 13-2(both blends containing the same rubber composition but in differentamounts and the rubbers prepared by different catalysis).

Although the invention has been described in considerable detail, thisdetail is for the purpose of illustration. Many variations andmodifications can be made on the invention as described above withoutdeparting from the spirit and scope of the invention as described in theappended claims. All publications identified above, specificallyincluding all U.S. patents and allowed U.S. patent applications, areincorporated in their entirety herein by reference.

1. An impact-resistant polymer blend comprising (i) a crystallinepolypropylene matrix comprising a blend of two or more polypropylenes atleast one of which has ¹³C NMR peaks corresponding to a regio-error atabout 14.6 and about 15.7 ppm, the peaks of about equal intensity, and(ii) a copolymer impact modifier comprising a blend of two or morepolymers at least one of which is an at least partially crystallinepropylene copolymer comprising propylene, ethylene and/or one or moreunsaturated comonomers prepared using a nonmetallocene, metal-centered,heteroaryl ligand catalyst, the at least partially crystalline propylenecopolymer having a percent crystallinity of about 40 to >0.
 2. Thepolymer blend of claim 1 in which at least one of the polypropylenes ofthe crystalline polypropylene matrix is a homopolymer.
 3. The polymerblend of claim 1 in which at least one of the polypropylenes of thecrystalline polypropylene matrix is a copolymer.
 4. The polymer blend ofclaim 1 in which the unsaturated comonomer is a C₄₋₂₀ α-olefin or diene.5. The polymer blend of claim 1 in which the at least partiallycrystalline propylene copolymer of the impact modifier blend is at leastone of a copolymer of propylene and ethylene or a terpolymer ofpropylene, ethylene and a C₄₋₂₀ α-olefin or diene.
 6. The polymer blendof claim 1 in which the at least partially crystalline propylenecopolymer of the impact modifier blend is characterized as (A)comprising at least about 60 weight percent (wt %) of units derived frompropylene, about 0.1-35 wt % of units derived from ethylene, and 0 toabout 35 wt % of units derived from one or more unsaturated comonomers,with the proviso that the combined weight percent of units derived fromethylene and the unsaturated comonomer does not exceed about
 40. 7. Thepolymer blend of claim 1 in which the at least partially crystallinepropylene copolymer of the impact modifier blend is characterized ascomprising at least about 60 weight percent (wt %) of units derived frompropylene and about 0.1-40 wt % of units derived from an unsaturatedcomonomer other than ethylene.
 8. The polymer blend of claim 1 in whichthe impact modifier blend has a melt flow rate of about 0.02 to 100 g/10min.
 9. The impact-resistant polymer blend of claim 8 in which thecrystalline polypropylene matrix blend comprises at least about 80percent by weight based upon the total weight of the impact-resistantpolymer blend.
 10. An article comprising the impact-resistant polymerblend of claim
 1. 11. An article comprising the impact-resistant polymerblend of claim
 6. 12. An article comprising the impact-resistant polymerblend of claim
 7. 13. A blow molded article comprising theimpact-resistant polymer blend of claim
 6. 14. A blow molded articlecomprising the impact-resistant polymer blend of claim
 7. 15. Theimpact-resistant polymer blend of claim 1 in which the MFR of the atleast partially crystalline copolymer impact modifier is at least 10times larger than the MFR of the crystalline polypropylene matrix. 16.The impact-resistant polymer blend of claim 1 in which the MFR of the atleast partially crystalline copolymer impact modifier is at least 30times larger than the MFR of the crystalline polypropylene matrix. 17.The impact-resistant polymer blend of claim 7 in which the MFR of the atleast partially crystalline copolymer impact modifier is at least 10times larger than the MFR of the crystalline polypropylene matrix. 18.The blend of claim 7 in which the MFR of the at least partiallycrystalline copolymer impact modifier is at least 30 times larger thanthe MFR of the crystalline polypropylene matrix.